CN107236139B - High-performance carbon nanotube/graphene oxide aerogel/polystyrene composite material and preparation method thereof - Google Patents
High-performance carbon nanotube/graphene oxide aerogel/polystyrene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-performance carbon nanotube/graphene oxide aerogel/polystyrene composite material. Firstly, preparing a graphene oxide suspension by an improved Hummers method, mixing the prepared graphene oxide with a carbon nano tube, and freeze-drying to prepare a carbon nano tube/graphene oxide aerogel; then filling a mixture containing styrene monomers into the gaps of the aerogel in a vacuum-assisted impregnation mode, obtaining a carbon nanotube/graphene oxide/polystyrene composite material through in-situ polymerization reaction, and finally carrying out heat treatment on the prepared composite material. The method has the advantages of simple process and environment-friendly process, the obtained skeleton aerogel has the advantages of low density, high porosity and the like, and the composite material obtained by compounding the skeleton aerogel with polystyrene has higher strength and modulus than pure polystyrene.
Description
Technical Field
The invention belongs to the technical field of nano porous materials-carbon aerogel, and also belongs to the field of advanced functional composite materials, and particularly relates to a high-performance carbon nanotube/graphene oxide aerogel/polystyrene composite material and a preparation method thereof.
Background
The aerogel is a porous nanomaterial with a three-dimensional network structure, a high specific surface area and a relatively low density, and can be regarded as not only a special functional material such as a nano skeleton, but also a new material state such as a condensed state. Therefore, the aerogel shows unique properties such as ultralow thermal conductivity, ultralow modulus, ultralow acoustic velocity, ultralow refractive index, ultralow dielectric constant, ultralow sound velocity and the like, and has wide application in many fields.
The graphene aerogel is the most studied aerogel in recent years, has unique performance, is widely applied to catalyst carriers, adsorption materials, hydrogen storage materials, electrode materials and the like, research and invention patents of compounding graphene and other materials to prepare the aerogel are reported in succession, and the prepared composite aerogel is applied to multiple fields. CN104558998A discloses a method for preparing graphene/polyimide-based carbon aerogel, which comprises mixing graphene and polyimide, freezing and drying to obtain an aerogel, and performing high-temperature carbonization to obtain the graphene/polyimide-based carbon aerogel, mainly used as a catalytic carrier, an electrode material of a hydrogen storage material-grade supercapacitor, and the like. Wangzhibao et al (preparation and conductivity of graphene aerogel/epoxy resin composite material, journal of composite material, 2013,30 (6): 1-6) studied that graphene oxide is used as a precursor, graphene aerogel is prepared by a sol-gel method, and then the graphene aerogel and epoxy resin are compounded in an ultrasonic mixing mode to prepare the graphene aerogel/epoxy resin composite material. Zeng Fan et al (Advanced multifunctionality graphene aerogel-Poly (methyl methacrylate) composites: Experiments and modules, Carbon,2015,81:396-404) graphene aerogel/polyester (methyl methacrylate) composites were prepared by backfilling polyester (methyl methacrylate) into the pores of the graphene aerogel, with multiple layers of reduced graphene oxide sheets uniformly distributed in the polyester (methyl methacrylate) matrix.
The patent and literature of the invention both disclose methods for preparing aerogel and composite material by compounding graphene and polymer, but the method for preparing composite material by compounding carbon nanotube/graphene oxide aerogel and polymer is rarely reported at present. Adding carbon nanotube powder into graphene oxide to carry out aerogel, and playing a certain supporting role on a stable structure of the graphene oxide, so that the agglomeration effect of the graphene oxide is weakened, and a larger specific surface area is obtained; in addition, the strength of the composite material can be improved by adding the carbon nano tubes.
The invention aims to select a proper thermosetting polymer material, utilize aerogel prepared from graphene oxide and carbon nanotubes as a framework material, fill the polymer into the pores of the three-dimensional network of the aerogel and cure the polymer under a vacuum condition, thereby preparing the high-performance composite material.
Disclosure of Invention
The invention aims to provide the aerogel and the method for compounding the aerogel and the styrene, wherein the preparation process is simple, the environment is protected, and the cost is lower; compared with other similar materials, the composite material prepared by the method has higher microhardness and compression modulus.
The technical scheme adopted by the invention is as follows:
a preparation method of a high-performance carbon nanotube/graphene oxide aerogel/polystyrene composite material comprises the following steps:
s1 preparation of carbon nanotube/graphene oxide aerogel
S1-1, preparing a graphene oxide suspension by adopting an improved Hummers method;
s1-2, respectively weighing the carbon nanotubes and the graphene oxide suspension prepared in the step S1-1, placing the carbon nanotubes and the graphene oxide suspension in a container, and performing ultrasonic dispersion for 3-4 hours to uniformly disperse the carbon nanotubes and the graphene oxide to obtain a dispersion liquid;
s1-3, subpackaging the dispersion liquid into weighing bottles, placing the weighing bottles in a refrigerator for pre-freezing for 11-13 hours, and then placing the pre-frozen gel in a freeze dryer for freeze drying for 36-60 hours to obtain the carbon nanotube/graphene oxide aerogel;
s2 preparation of carbon nanotube/graphene oxide aerogel/polystyrene composite material
S2-1, mixing and uniformly stirring a styrene monomer and an azodiisobutyronitrile initiator to obtain a prepolymer mixed solution;
s2-2, dropwise adding the prepolymer mixed liquid prepared in the step S2-1 into the aerogel prepared in the step S1, and filling all gaps of the aerogel with the mixture in a vacuum auxiliary impregnation mode;
s2-3, heating the aerogel filled with the prepolymer mixed solution to perform in-situ polymerization reaction on the carbon nanotube/graphene oxide aerogel and a styrene monomer, and obtaining the carbon nanotube/graphene oxide aerogel/polystyrene composite material after the reaction;
s3, heat treatment of carbon nanotube/graphene oxide aerogel/polystyrene composite material
And (4) putting the carbon nanotube/graphene oxide aerogel/polystyrene composite material prepared in the step (S2) into a mold, heating to the glass transition temperature of polystyrene, pressurizing, compressing the composite material by 10% of the height, and naturally cooling to room temperature.
The specific steps of preparing the graphene oxide suspension by adopting the improved Hummers method in the step S1-1 are as follows:
s1-11, mixing graphite and sodium nitrate into a container filled with concentrated sulfuric acid, mechanically stirring for 0.5-1 h in an ice bath, adding potassium permanganate, continuously stirring for 2-2.5h in the ice bath, raising the temperature of the water bath to 25-35 ℃, continuously stirring for 10-14 h, slowly adding deionized water twice, then adding a hydrogen peroxide solution, and finally ultrasonically stripping for 30-60 min to obtain a graphene oxide mixture;
s1-12, adding a hydrochloric acid solution into the mixture prepared in the step S1-11, mechanically centrifuging for 15-30 min, then washing with deionized water until the centrifuged supernatant is neutral, and finally preparing graphene oxide suspension from the lower-layer precipitated graphene oxide.
In the step S1-11, the mass ratio of graphite, sodium nitrate, concentrated sulfuric acid, potassium permanganate and deionized water is 2 (0.8-1): 160-170): 5-6): 260-270); the volume concentration of the hydrogen peroxide solution is 30 percent; the volume ratio of the added deionized water to the hydrogen peroxide solution is (50-55) to (2-2.5).
The concentration of concentrated sulfuric acid added in the steps S1-11 and S1-12 is 98%, the concentration of hydrochloric acid is 1.5-2.1 mol/L, and the concentration of the prepared graphene oxide water suspension is 8-16 mg/mL.
The carbon nanotube is a carbon nanotube which is modified by oxidation so that the surface thereof has 4-6% of carboxyl groups and 6-8% of hydroxyl functional groups (the percentage of carboxyl groups and hydroxyl groups in the carbon nanotube is the mass percentage based on the carbon nanotube after oxidation, for example, the carbon nanotube after oxidation is 100g, and contains 4-6 g of carboxyl groups and 6-8 g of hydroxyl functional groups).
In the step S1-2, the mass ratio of the carbon nano tube to the graphene oxide is (0-1): 1-0.
In the step S1-2, the weighed carbon nanotubes should be ultrasonically dispersed in water for 30-50 min, and then mixed with the graphene oxide suspension.
The amount of the styrene monomer and the azodiisobutyronitrile added in the step S2 needs to submerge the carbon nanotube/graphene oxide aerogel, and the mass ratio of the styrene monomer to the azodiisobutyronitrile is 20: (0.06-0.1).
The polymerization reaction in the step S2-3 is carried out at the reaction temperature of 80-100 ℃ for 24-48 h.
In the step S3, the heating temperature is 90-100 ℃, and the pressurizing pressure is 10-20 MPa.
A high-performance carbon nano tube/graphene oxide aerogel/polystyrene composite material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the carbon nanotube/graphene oxide aerogel prepared by the invention is prepared by uniformly mixing graphene oxide and self-made modified carbon nanotubes in a certain proportion and performing freeze drying. The mechanical property of the aerogel is enhanced by adding the carbon nano tubes, so that the graphene oxide sheet layer is built more stably, the aerogel is not easy to collapse when the polymer is filled, and meanwhile, the filling rate of the polymer is improved. The graphene oxide particles have a certain supporting effect on a stable structure, so that the agglomeration effect of the graphene oxide is weakened, and a larger specific surface area is obtained. The added carbon nano tube is an oxidation modified carbon nano tube, the surface of the modified carbon nano tube has a large amount of carboxyl and hydroxyl functional groups, and the modified carbon nano tube can react with functional groups in graphene oxide and polystyrene during compounding, so that the combination is firmer, and the mechanical property of the composite material is improved.
(2) The composite material framework is the carbon nano tube/graphene oxide aerogel, the carbon nano tube/graphene oxide aerogel has a three-dimensional network pore structure with mesopores, micropores and macropores, higher strength and high specific surface area, the composite material obtained after the composite material is compounded with polystyrene has higher strength and modulus than pure polystyrene, in the prepared composite material, the graphene oxide aerogel is uniformly dispersed in the polystyrene, the content of the carbon nano tube and the graphene oxide aerogel is only 0.57 wt%, but the microhardness of the composite material is improved by more than 3 times than that of the pure styrene, and the compression modulus is also enhanced by more than 300 MPa.
(3) In the invention, the mass ratio of styrene to Azodiisobutyronitrile (AIBN) is 20: (0.06-0.1), and directly polymerizing in situ in the aerogel without prepolymerization, so that the formation of bubbles in the prepolymerization process is avoided.
(4) After the composite material is prepared, in order to eliminate micropores generated by the closed pore phenomenon of the aerogel in the composite material, the composite material is subjected to heat treatment, and the composite material after the heat treatment can shield a small amount of closed pore phenomenon, so that the composite material has higher density, microhardness and compression modulus than the composite material before the heat treatment.
(5) The preparation process of the invention is simple, environment-friendly, easy to operate, and has low requirements on equipment and operators, thus being a relatively environment-friendly chemical preparation method.
Drawings
FIG. 1 is an infrared spectrum of graphite and graphene oxide;
FIG. 2 is a scanning electron microscope image of a carbon nanotube/graphene oxide aerogel and a carbon nanotube/graphene oxide aerogel/polystyrene composite material;
fig. 3 is a compressive stress-strain curve for polystyrene, graphene oxide aerogel/polystyrene, and carbon nanotube/graphene oxide aerogel/polystyrene;
fig. 4 is a graph of fiber hardness for polystyrene, graphene oxide aerogel/polystyrene, and carbon nanotube/graphene oxide aerogel/polystyrene.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below. This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art, and the present invention will only be defined by the appended claims.
Example 1:
the preparation method of the carbon nanotube/graphene oxide aerogel/polystyrene composite material in this embodiment includes the following steps:
s0, preparing graphene oxide suspension by adopting improved Hummers method
S0-1, weighing 8g of graphite and 3.5g of sodium nitrate according to requirements, mixing the graphite and the sodium nitrate into a three-neck flask filled with 360mL of 98% concentrated sulfuric acid, mechanically stirring the mixture in an ice bath for 1h, then adding 20g of potassium permanganate, continuously stirring the mixture in the ice bath for 2h, raising the temperature of the water bath to 35 ℃, continuously stirring the mixture for 14 h, slowly adding 1050mL of deionized water in two times, finally adding 50mL of 30% hydrogen peroxide solution by volume concentration, reacting the mixture for 30min, and finally ultrasonically stripping the mixture for 30min under 30KHz ultrasonic frequency to obtain a graphene oxide mixture;
s0-2, adding a hydrochloric acid solution with the concentration of 1.5mol/L into the graphene oxide mixture, centrifuging for 15min at 9000r/min, then washing with deionized water until the centrifuged supernatant is neutral, and finally preparing graphene oxide suspension with the concentration of 16mg/mL from the graphene oxide precipitated at the lower layer;
s1 preparation of carbon nanotube/graphene oxide aerogel
S1-1, respectively weighing 0.24g of carbon nanotubes according to the mass ratio of 1:1 and 60ml of graphene oxide suspension prepared in the step S0, firstly placing the weighed carbon nanotubes in a beaker containing deionized water in water for ultrasonic dispersion for 30min, then mixing the carbon nanotubes with the graphene oxide suspension, and performing ultrasonic dispersion for 3h to ensure that the carbon nanotubes and the graphene oxide are uniformly dispersed, wherein the ultrasonic frequency of the ultrasonic dispersion is 30 KHz; the selected carbon nanotube is a surface oxidation modified carbon nanotube, the surface of the carbon nanotube has 4-6% of carboxyl and 6-8% of hydroxyl functional groups by mass ratio, and the carbon nanotube can react with functional groups in graphene oxide and polystyrene during compounding, so that the combination is firmer, and the mechanical property of the composite material is improved.
S1-2, quickly subpackaging the dispersed samples into weighing bottles, placing the weighing bottles in a refrigerator for pre-freezing for 12 hours, and then placing the frozen gel in a freeze dryer for freeze drying for 48 hours to obtain the carbon nanotube/graphene oxide aerogel;
s2 preparation of carbon nanotube/graphene oxide aerogel/polystyrene composite material
S2-1, weighing 20g of styrene monomer and 0.08g of azodiisobutyronitrile initiator, pouring into a beaker, mixing and stirring uniformly;
s2-2, dripping the mixture of the monomers and the initiator mixed in the step S2-1 into the aerogel prepared in the step S1, submerging the aerogel, putting the aerogel into a vacuum device in a vacuum-assisted impregnation mode, and completely immersing the mixture into micropores of the aerogel under the pressure of-100 KPa;
s2-3, carrying out in-situ polymerization reaction on the aerogel filled with the styrene monomer at 80-100 ℃ for 24h to obtain the carbon nano tube/graphene oxide aerogel/polystyrene composite material.
S3, heat treatment of carbon nanotube/graphene oxide aerogel/polystyrene composite material
In order to eliminate the few micropores generated in the composite material due to the closed pore phenomenon of the aerogel, the carbon nanotube/graphene oxide aerogel/polystyrene composite material prepared in the step S2 is placed in a mold, heated to the glass transition temperature (90-100 ℃) of polystyrene, then applied with 20MPa pressure, compressed to 10% of the height of the composite material, and naturally cooled to room temperature, so as to obtain the required carbon nanotube/graphene oxide aerogel/polystyrene composite material.
The inventors of the present invention analyzed the infrared spectrograms of graphite and graphene oxide by fourier transform infrared spectroscopy, as shown in fig. 1, in which curve 1 represents the infrared spectrogram of graphite and curve 2 represents the infrared spectrogram of graphene oxide. The result shows that the perfect graphite does not contain any functional group, after the perfect graphite is oxidized into graphene oxide, the surface of the perfect graphite contains functional groups such as hydroxyl, carboxyl, carbonyl and the like, and the functional group structure of the graphene oxide can be represented by infrared spectroscopy. The oxygen-containing functional groups have good hydrophilicity, so that the graphene oxide can be stably dispersed in an aqueous solution, and can also perform chemical reaction with the functional groups on the surface of the carbon nano tube, thereby greatly improving the interaction force among substances, enabling the aerogel framework to be more stable, and having better mechanical properties.
In order to characterize the microstructure of the obtained carbon nanotube/graphene oxide aerogel/polystyrene composite material, a scanning electron microscope is used to analyze the microstructure of the carbon nanotube/graphene oxide aerogel/polystyrene composite material, as shown in fig. 2, fig. 2(a) is a scanning electron microscope image of the carbon nanotube/graphene oxide aerogel, and fig. 2(b) is a scanning electron microscope image of the carbon nanotube/graphene oxide aerogel/polystyrene composite material. The result shows that the aerogel which is not filled with styrene contains more pore structures, graphene oxide sheets are mutually built together, and formed micropores are relatively uniform; after the polystyrene is filled, the polystyrene is completely immersed in the pores of the carbon nanotube/graphene oxide aerogel, and the polystyrene is more densely filled in the aerogel.
Fig. 3 shows compressive stress-strain curves of three materials, namely polystyrene, graphene oxide aerogel/polystyrene and carbon nanotube/graphene oxide aerogel/polystyrene composite, wherein curve 1 represents the compressive stress-strain curve of polystyrene, curve 2 represents the compressive stress-strain curve of carbon nanotube/graphene oxide aerogel/polystyrene composite, and curve 3 represents the compressive stress-strain curve of graphene oxide aerogel/polystyrene. As can be clearly seen from the figure, when the strain is between 0% and 10%, the compressive modulus of the nanotube/graphene oxide aerogel/polystyrene composite material prepared in this embodiment is greater than that of the graphene oxide aerogel/polystyrene composite material and pure polystyrene.
Figure 4 gives the microhardness of polystyrene, graphene oxide aerogel/polystyrene and carbon nanotube/graphene oxide aerogel/polystyrene. It can be seen from the figure that the microhardness of the carbon nanotube/graphene oxide aerogel/polystyrene composite material prepared by the embodiment is more than four times of that of polystyrene, and is higher than that of graphene oxide aerogel/polystyrene.
TABLE 1 comparison of polystyrene, graphene oxide aerogel/polystyrene and carbon nanotube/graphene oxide aerogel/polystyrene Properties
Table 1 compares the performances of three materials, namely polystyrene, graphene oxide aerogel/polystyrene and carbon nanotube/graphene oxide aerogel/polystyrene, and from the analysis of actual density and theoretical density in the table, it can be seen that the filling rate of the carbon nanotube/graphene oxide aerogel/polystyrene composite material prepared in this embodiment is 98.04% which is the maximum, and the filling rate of the graphene oxide aerogel/polystyrene composite material without adding carbon nanotube is 96.40%, which is lower than the filling rate of the carbon nanotube/graphene oxide aerogel/polystyrene composite material, and the carbon nanotube plays a certain supporting role in the aerogel, so that the aerogel has a better three-dimensional network structure, and is convenient for filling a polymer; the content of the carbon nano tube and the graphene oxide is low (only accounting for 0.57 wt% of the composite material), but the mechanical property of the composite material is greatly improved, the microhardness of the composite material is improved by more than 3 times compared with that of pure styrene, and the compression modulus is also enhanced by more than 300 MPa.
Example 2:
the preparation method of the carbon nanotube/graphene oxide aerogel/polystyrene composite material in this embodiment includes the following steps:
s0, preparing graphene oxide suspension by adopting improved Hummers method
S0-1, weighing 8g of graphite and 4g of sodium nitrate according to requirements, mixing the graphite and the sodium nitrate into a three-neck flask containing 350mL of 98% concentrated sulfuric acid, mechanically stirring the mixture in an ice bath for 1h, then adding 24g of potassium permanganate, continuously stirring the mixture in the ice bath for 2h, raising the temperature of the water bath to 25 ℃, continuously stirring the mixture for 10 h, slowly adding 1080mL of deionized water twice, finally adding 50mL of 30% hydrogen peroxide solution by volume concentration, reacting the mixture for 30min, and finally ultrasonically stripping the mixture for 60min under 30KHz ultrasonic frequency to obtain a graphene oxide mixture;
s0-2, adding a hydrochloric acid solution with the concentration of 1.7mol/L into the graphene oxide mixture, centrifuging for 30min at 9000r/min, then washing with deionized water until the centrifuged supernatant is neutral, and finally preparing graphene oxide suspension with the concentration of 8mg/mL from the graphene oxide precipitated at the lower layer;
s1 preparation of carbon nanotube/graphene oxide aerogel
S1-1, respectively weighing 0.12g of carbon nanotubes according to the mass ratio of 0.5:1 and 30ml of graphene oxide suspension prepared in the step S0, firstly placing the weighed carbon nanotubes in a beaker containing deionized water in water for ultrasonic dispersion for 40min, then mixing the carbon nanotubes with the graphene oxide suspension, and performing ultrasonic dispersion for 5h to ensure that the carbon nanotubes and the graphene oxide are uniformly dispersed, wherein the ultrasonic frequency of the ultrasonic dispersion is 40 KHz; the selected carbon nano tube is a carbon nano tube subjected to surface oxidation modification, the surface of the carbon nano tube has 4-6% of carboxyl groups and 6-8% of hydroxyl functional groups in mass ratio, and the carbon nano tube can react with the functional groups in graphene oxide and polystyrene during compounding, so that the combination is firmer, and the mechanical property of the composite material is improved.
S1-2, quickly subpackaging the dispersed samples into weighing bottles, placing the weighing bottles in a refrigerator for pre-freezing for 12 hours, and then placing the pre-frozen gel in a freeze dryer for freeze drying for 48 hours to obtain the carbon nanotube/graphene oxide aerogel;
s2 preparation of carbon nanotube/graphene oxide aerogel/polystyrene composite material
S2-1, weighing 20g of styrene monomer and 0.1g of azodiisobutyronitrile initiator, pouring into a beaker, mixing and stirring uniformly;
s2-2, dripping the mixture of the monomers and the initiator mixed in the step S2-1 into the aerogel prepared in the step S1, submerging the aerogel, putting the aerogel into a vacuum device in a vacuum-assisted impregnation mode, and completely immersing the mixture into micropores of the aerogel under the pressure of-100 KPa;
s2-3, carrying out in-situ polymerization reaction on the aerogel filled with the styrene monomer at 80-100 ℃ for 48h to obtain the carbon nano tube/graphene oxide aerogel/polystyrene composite material.
S3, heat treatment of carbon nanotube/graphene oxide aerogel/polystyrene composite material
In order to eliminate the few micropores generated in the composite material due to the closed pore phenomenon of the aerogel, the carbon nanotube/graphene oxide aerogel/polystyrene composite material prepared in the step S2 is placed in a mold, heated to the glass transition temperature (90-100 ℃) of polystyrene, then applied with 10MPa pressure, compressed to 10% of the height of the composite material, and naturally cooled to room temperature, so as to obtain the required carbon nanotube/graphene oxide aerogel/polystyrene composite material.
Example 3:
the preparation method of the carbon nanotube/graphene oxide aerogel/polystyrene composite material in this embodiment includes the following steps:
s0, preparing graphene oxide suspension by adopting improved Hummers method
S0-1, weighing 4g of graphite and 1.9g of sodium nitrate according to requirements, mixing the graphite and the sodium nitrate into a three-neck flask filled with 180mL of 98% concentrated sulfuric acid, mechanically stirring the mixture in an ice bath for 1h, then adding 11g of potassium permanganate, continuously stirring the mixture in the ice bath for 2h, raising the temperature of the water bath to 30 ℃, continuously stirring the mixture for 12h, slowly adding 540mL of deionized water twice, finally adding 20mL of 30% hydrogen peroxide solution by volume concentration, reacting the mixture for 60min, and finally ultrasonically stripping the mixture for 30min under 40KHz ultrasonic frequency to obtain a graphene oxide mixture;
s0-2, adding a hydrochloric acid solution with the concentration of 1.6mol/L into the graphene oxide mixture, centrifuging for 30min at 9000r/min, then washing with deionized water until the centrifuged supernatant is neutral, and finally preparing graphene oxide suspension with the concentration of 8mg/mL from the graphene oxide precipitated at the lower layer;
s1 preparation of carbon nanotube/graphene oxide aerogel
S1-1, respectively weighing 0.24g of carbon nanotubes according to the mass ratio of 1:0.5 and 15ml of graphene oxide suspension prepared in the step S0, firstly placing the weighed carbon nanotubes in a beaker containing deionized water in water for ultrasonic dispersion for 50min, then mixing the carbon nanotubes with the graphene oxide suspension, and performing ultrasonic dispersion for 4h to ensure that the carbon nanotubes and the graphene oxide are uniformly dispersed, wherein the ultrasonic frequency of the ultrasonic dispersion is 35 KHz; the selected carbon nano tube is a carbon nano tube subjected to surface oxidation modification, the surface of the carbon nano tube has 4-6% of carboxyl groups and 6-8% of hydroxyl functional groups in mass ratio, and the carbon nano tube can react with the functional groups in graphene oxide and polystyrene during compounding, so that the combination is firmer, and the mechanical property of the composite material is improved.
S1-2, quickly subpackaging the dispersed samples into weighing bottles, placing the weighing bottles in a refrigerator for pre-freezing for 12 hours, and then placing the pre-frozen gel in a freeze dryer for freeze drying for 36 hours to obtain the carbon nanotube/graphene oxide aerogel;
s2 preparation of carbon nanotube/graphene oxide aerogel/polystyrene composite material
S2-1, weighing 20g of styrene monomer and 0.06g of azodiisobutyronitrile initiator, pouring into a beaker, mixing and stirring uniformly;
s2-2, dripping the mixture of the monomers and the initiator mixed in the step S2-1 into the aerogel prepared in the step S1, submerging the aerogel, putting the aerogel into a vacuum device in a vacuum-assisted impregnation mode, and completely immersing the mixture into micropores of the aerogel under the pressure of-100 KPa;
s2-3, carrying out in-situ polymerization reaction on the aerogel filled with the styrene monomer at 80-100 ℃ for 36h to obtain the carbon nano tube/graphene oxide aerogel/polystyrene composite material.
S3, heat treatment of carbon nanotube/graphene oxide aerogel/polystyrene composite material
In order to eliminate the few micropores generated in the composite material due to the closed pore phenomenon of the aerogel, the carbon nanotube/graphene oxide aerogel/polystyrene composite material prepared in the step S2 is placed in a mold, heated to the glass transition temperature (90-100 ℃) of polystyrene, then applied with 15MPa pressure, compressed to 10% of the height of the composite material, and naturally cooled to room temperature, so as to obtain the required carbon nanotube/graphene oxide aerogel/polystyrene composite material.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to be within the scope of the invention.
Claims (10)
1. A preparation method of a high-performance carbon nanotube/graphene oxide aerogel/polystyrene composite material is characterized by comprising the following steps:
s1 preparation of carbon nanotube/graphene oxide aerogel
S1-1, preparing a graphene oxide suspension by adopting an improved Hummers method;
s1-2, respectively weighing the carbon nanotubes and the graphene oxide suspension prepared in the step S1-1, placing the carbon nanotubes and the graphene oxide suspension in a container, and performing ultrasonic dispersion for 3-4 hours to uniformly disperse the carbon nanotubes and the graphene oxide to obtain a dispersion liquid;
s1-3, subpackaging the dispersion liquid into weighing bottles, placing the weighing bottles in a refrigerator for pre-freezing for 11-13 hours, and then placing the pre-frozen gel in a freeze dryer for freeze drying for 36-60 hours to obtain the carbon nanotube/graphene oxide aerogel;
s2 preparation of carbon nanotube/graphene oxide aerogel/polystyrene composite material
S2-1, mixing and uniformly stirring a styrene monomer and an azodiisobutyronitrile initiator to obtain a prepolymer mixed solution;
s2-2, dropwise adding the prepolymer mixed liquid prepared in the step S2-1 into the aerogel prepared in the step S1, and filling all gaps of the aerogel with the mixture in a vacuum auxiliary impregnation mode;
s2-3, heating the aerogel filled with the prepolymer mixed solution to perform in-situ polymerization reaction on the carbon nanotube/graphene oxide aerogel and a styrene monomer, and obtaining the carbon nanotube/graphene oxide aerogel/polystyrene composite material after the reaction;
s3, heat treatment of carbon nanotube/graphene oxide aerogel/polystyrene composite material
Putting the carbon nanotube/graphene oxide aerogel/polystyrene composite material prepared in the step S2 into a mold, heating to the glass transition temperature of polystyrene, pressurizing, compressing the composite material by 10% of the height, and naturally cooling to room temperature;
the specific steps of preparing the graphene oxide suspension by adopting the improved Hummers method in the step S1-1 are as follows:
s1-11, mixing graphite and sodium nitrate into a container filled with concentrated sulfuric acid, mechanically stirring for 0.5-1 h in an ice bath, adding potassium permanganate, continuously stirring for 2-2.5h in the ice bath, raising the temperature of the water bath to 25-35 ℃, continuously stirring for 10-14 h, slowly adding deionized water twice, then adding a hydrogen peroxide solution, and finally ultrasonically stripping for 30-60 min to obtain a graphene oxide mixture;
s1-12, adding a hydrochloric acid solution into the mixture prepared in the step S1-11, mechanically centrifuging for 15-30 min, then washing with deionized water until the centrifuged supernatant is neutral, and finally preparing graphene oxide suspension from the lower-layer precipitated graphene oxide.
2. The method for preparing a carbon nanotube/graphene oxide aerogel/polystyrene composite material according to claim 1, wherein the mass ratio of graphite, sodium nitrate, concentrated sulfuric acid, potassium permanganate and deionized water in step S1-11 is 2 (0.8-1): 160-170): 5-6): 260-270); the volume concentration of the hydrogen peroxide solution is 30 percent; the volume ratio of the added deionized water to the hydrogen peroxide solution is (50-55) to (2-2.5).
3. The method for preparing a carbon nanotube/graphene oxide aerogel/polystyrene composite material according to claim 2, wherein the concentrated sulfuric acid added in the steps S1-11 and S1-12 has a concentration of 98%, the hydrochloric acid has a concentration of 1.5 to 2.1mol/L, and the prepared graphene oxide aqueous suspension has a concentration of 8 to 16 mg/mL.
4. The method for preparing the carbon nanotube/graphene oxide aerogel/polystyrene composite material according to claim 3, wherein the carbon nanotube is modified by oxidation so that the surface of the carbon nanotube has 4-6% of carboxyl groups and 6-8% of hydroxyl functional groups by mass.
5. The method for preparing the carbon nanotube/graphene oxide aerogel/polystyrene composite material according to claim 4, wherein the mass ratio of the carbon nanotube to the graphene oxide in the step S1-2 is (0-1): (1-0).
6. The method for preparing the carbon nanotube/graphene oxide aerogel/polystyrene composite material according to claim 5, wherein in the step S1-2, the weighed carbon nanotubes are ultrasonically dispersed in water for 30-50 min, and then mixed with the graphene oxide suspension.
7. The method for preparing a carbon nanotube/graphene oxide aerogel/polystyrene composite material according to claim 6, wherein the styrene monomer and the azobisisobutyronitrile added in the step S2 are required to submerge the carbon nanotube/graphene oxide aerogel, and the mass ratio of the styrene monomer to the azobisisobutyronitrile is 20: (0.06-0.1).
8. The method for preparing a carbon nanotube/graphene oxide aerogel/polystyrene composite material according to claim 7, wherein the polymerization reaction in the step S2-3 is performed at a reaction temperature of 80-100 ℃ for 24-48 h.
9. The method for preparing the carbon nanotube/graphene oxide aerogel/polystyrene composite material according to claim 8, wherein the method comprises the following steps: in the step S3, the heating temperature is 90-100 ℃, and the pressurizing pressure is 10-20 MPa.
10. A high performance carbon nanotube/graphene oxide aerogel/polystyrene composite prepared by the method of any one of claims 1 to 9.
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