CN110562963A - preparation method of graphene-carbon nanotube hybrid sponge - Google Patents
preparation method of graphene-carbon nanotube hybrid sponge Download PDFInfo
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Abstract
The invention provides a preparation method of a graphene-carbon nanotube hybrid sponge, which comprises the following steps: preparing carbon nanotube sponge; preparing polystyrene microspheres; preparing graphene oxide coated polystyrene microspheres; dispersing the graphene-coated polystyrene microspheres into an aqueous solution, pouring the aqueous solution into carbon nanotube sponge in vacuum, and then obtaining a graphene/polystyrene microsphere/carbon nanotube sponge material by adopting a freeze drying method; and heating the obtained graphene/polystyrene microsphere/carbon nanotube sponge material to remove the polystyrene microsphere and reduce the oxidized graphene to obtain the graphene-carbon nanotube hybrid sponge. According to the technical scheme, the carbon nanotube sponge is used as a precursor, the graphene-carbon nanotube hybrid sponge is prepared by adopting a vacuum infusion method, and the graphene is introduced into the carbon nanotube sponge, so that the specific surface area of the reinforcement is increased, the conductivity of the carbon nanotube sponge is improved, and the electromagnetic shielding effect is improved.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a preparation method of graphene-carbon nanotube hybrid sponge.
Background
The 20 th century is a century of rapid development of modern science and technology, and one of the important signs is the magnificent achievement of human beings in the aerospace field. In the 21 st century, aerospace has shown a wider development prospect, and high-level or ultra-high-level aerospace activities are more frequent, the effects of the aerospace are far beyond the scientific and technical field, and the aerospace has wider and more profound effects on political, economic, military and even human social life. It should be noted that the great achievements achieved by the aerospace industry are not separable from the development and breakthrough of aerospace materials technology. The material is the foundation and the precursor of modern high and new technology and industry, and is a precondition for breakthrough of the high and new technology to a great extent. The general development trend of materials is light weight, high strength, high modulus, high temperature resistance and low cost, and the structure-function integration and intellectualization are more important material development directions due to the development requirements of modern high-performance aircrafts.
The carbon nanotube sponge is a nano carbon macroscopic body formed by mutually staggered, lapped and communicated carbon nanotubes. However, the carbon nanotube itself has a one-dimensional structure, and is limited by space in the process of further improving the performance, so that the application of the carbon nanotube sponge is greatly limited. The graphene is known to researchers who obtain the Nobel prize in 2010, the graphene has excellent mechanical, electrical and thermal properties, and if the carbon nanotube sponge and the graphene can be combined, the single-dimensional limitation is broken through, a carbon nanotube-graphene macroscopic body combined in a cross-dimension mode is obtained, and structural innovation and function expansion are achieved. However, graphene is difficult to be introduced into carbon nanotube sponge, and examples of introducing graphene into carbon nanotube sponge are only reported and limited in application.
disclosure of Invention
Aiming at the technical problems, the invention discloses a preparation method of graphene-carbon nanotube hybrid sponge, which solves the problems that the existing method can not introduce graphene into the carbon nanotube sponge, improves the electrical properties and the like of the carbon nanotube sponge, expands the functional application of the carbon nanotube sponge, and has more advantages in electrical conductivity compared with other hybrid sponges.
In contrast, the technical scheme adopted by the invention is as follows:
A preparation method of a graphene-carbon nanotube hybrid sponge is characterized by comprising the following steps:
Step S1, preparing carbon nanotube sponge;
step S2, preparing polystyrene microspheres;
Step S3, preparing graphene oxide coated polystyrene microspheres;
Step S4, dispersing the graphene-coated polystyrene microspheres into an aqueous solution, filling the aqueous solution into the carbon nanotube sponge in vacuum, and then obtaining a graphene/polystyrene microsphere/carbon nanotube sponge material by adopting a freeze drying method;
Step S5, heating the obtained graphene/polystyrene microsphere/carbon nanotube sponge material to remove the polystyrene microsphere and reduce the graphene oxide to obtain the graphene-carbon nanotube hybrid sponge.
According to the technical scheme, the graphene oxide/polystyrene microsphere/carbon nanotube sponge material is prepared by adopting a vacuum infusion method, the high-performance graphene-carbon nanotube hybrid sponge is prepared by utilizing a one-step heat treatment method, and SEM of the graphene oxide-carbon nanotube hybrid sponge proves that graphene is introduced into the carbon nanotube sponge. The obtained graphene-carbon nanotube hybrid sponge has special edge effect, good compression performance, high specific surface area and low defect, and solves the problems of the graphene sponge prepared by the existing method in the aspects of interface, dispersion and mechanical property.
Further, the carbon nanotube sponge is prepared by adopting a chemical vapor deposition method.
furthermore, the polystyrene microspheres are prepared by a dispersion polymerization method.
Further, the graphene oxide coated polystyrene ball is prepared by using polystyrene microspheres as a removable template and graphene oxide nanosheets as a shell building unit and coating the graphene oxide nanosheets through a layer-by-layer self-assembly method (LBL assembly) to obtain the graphene oxide coated polystyrene ball.
As a further improvement of the invention, the preparation of the carbon nanotube sponge in step S1 comprises dissolving catalyst ferrocene in liquid carbon source 1, 2-dichlorobenzene to obtain catalyst/carbon source solution, injecting the catalyst/carbon source solution into the preheating zone of the tube furnace for vaporization, and evaporating H2the/Ar carrier gas brings the carbon source and the catalyst into the reaction zone of the tubular furnace to react to form the carbon nanotube sponge.
As a further improvement of the invention, the proportion of the catalyst/carbon source solution is that 5-30g of ferrocene powder is dissolved in every 90-300ml of 1, 2-dichlorobenzene; the temperature of the preheating zone is 180-450 ℃, and the temperature of the reaction zone is 700-1200 ℃. Further, the temperature of the preheating zone is 180-400 ℃.
As a further improvement of the invention, the temperature of the preheating zone is 200-400 ℃, and the temperature of the reaction zone is 800-1000 ℃.
as a further improvement of the invention, said H2h in/Ar carrier gas2The volume ratio of/Ar is 1:1-1:4, and the flow rate of carrier gas is 400-2000 mL/min.
as a further improvement of the invention, the preparation of the polystyrene microspheres in step S2 comprises dissolving an initiator in a styrene monomer, adding the initiator into a polyvinylpyrrolidone solution under the environment of nitrogen or inert gas, stirring, heating to 60 ~ 80 ℃ for polymerization reaction for 5 ~ 48 h to obtain a polystyrene emulsion sample, cooling the polystyrene emulsion sample to room temperature, then carrying out centrifugal treatment, washing, and carrying out vacuum drying on the obtained white solid at 40 ~ 55 ℃ to obtain the polystyrene microspheres.
Further, the initiator is azobisisobutyronitrile.
Further, the preparation of the polyvinylpyrrolidone solution comprises: and mixing the polyvinylpyrrolidone with the ethanol-water mixed solvent, and stirring until the PVP solid is completely dissolved to obtain a polyvinylpyrrolidone solution. Wherein the mass ratio of the polyvinylpyrrolidone to the ethanol to the water is as follows: 0.1-10: 100-500: 5-100.
further, the conditions of the centrifugation treatment are as follows: the rotating speed is 1000-9000 rpm, and the time is 1-30 min.
Further, washing was performed with ethanol.
As a further improvement of the present invention, step S3 includes: dispersing polystyrene microspheres into a polyethyleneimine aqueous solution, adjusting the pH of a reaction system to 9-12, stirring and ultrasonically dispersing for 0.5-2.5h to obtain a reaction dispersion, and performing centrifugal separation and washing on the reaction dispersion to obtain polyethyleneimine-coated polystyrene microspheres;
Dispersing the polystyrene microspheres coated with polyethyleneimine into deionized water to obtain a dispersion liquid, adjusting the pH of the dispersion liquid to 9-12, and performing ultrasonic treatment; and dropwise adding the prepared graphene oxide aqueous solution into the dispersion liquid, and then carrying out centrifugal washing to obtain the graphene oxide-coated polystyrene microsphere.
As a further improvement of the invention, the concentration of PEI in the polyethyleneimine aqueous solution is 5-15 mg/mL; the dosage of the polystyrene microspheres and the polyethyleneimine aqueous solution is that each 0.1-10 g of the polystyrene microspheres are dispersed into 200-500mL of the polyethyleneimine aqueous solution.
As a further improvement of the invention, the concentration of the graphene oxide aqueous solution is 0.0001-0.003 mg/ml.
as a further improvement of the present invention, step S4 includes: dispersing the prepared graphene oxide coated polystyrene microspheres into an aqueous solution to prepare a suspension of 5-100mg/ml, pouring the suspension into carbon nanotube sponge of 1-100mg by a vacuum pouring method, and finally preparing the graphene oxide/polystyrene spheres/carbon nanotube sponge material by a freeze drying method.
as a further improvement of the invention, the vacuum degree of the vacuum infusion is-0.1 MPa-1 MPa.
As a further improvement of the present invention, in step S5, the temperature of the heat treatment is 300 ℃ to 1200 ℃.
As a further improvement of the present invention, in step S5, the temperature of the heat treatment is 300 ℃ to 800 ℃.
more specifically, the preparation method of the graphene-carbon nanotube hybrid sponge comprises the following steps:
Firstly, preparing carbon nanotube sponge: preparing the carbon nanotube sponge by adopting a chemical vapor deposition method: ultrasonically dissolving a catalyst ferrocene in a liquid carbon source 1, 2-dichlorobenzene to obtain a catalyst/carbon source solution, and preparing 5-30g of ferrocene powder in every 90-300ml of 1, 2-dichlorobenzene in a ratio; the catalyst/carbon source solution is injected into the preheating zone of the tube furnace by a precise injection pump to be quickly vaporized, H2carrying a carbon source and a catalyst into a reaction zone of the tubular furnace by using/Ar carrier gas to generate, grow and stack carbon nanotube sponge; the temperature of the preheating zone is 180-450 ℃, and the temperature of the high-temperature reaction zone is 700-1200 ℃; said H2Ar carrier gas, H2The volume ratio of/Ar is 1:1-1:4, and the flow rate of carrier gas is 400-2000 mL/min.
Secondly, preparing Polystyrene (PS) balls: firstly, 0.1-10 g of polyvinylpyrrolidone (PVP) and ethanol-water mixed solvent (100-500 g of ethanol and 5-100 g of deionized water) are added into a three-necked bottle, magnetic stirring is carried out until PVP solid is completely dissolved, and nitrogen is introduced to exhaust air in the bottle. Dissolving 0.1-5g of Azodiisobutyronitrile (AIBN) in 1-100 g of styrene monomer, slowly dripping into a reaction system, heating to 60-80 ℃ under the protection of nitrogen and at a certain stirring speed, and carrying out polymerization reaction for 5-48 h to obtain a polystyrene emulsion sample. After the reaction system is cooled to room temperature, carrying out centrifugal treatment on the emulsion sample (1000-9000 rpm, 1-30 min), washing for 1-10 times by using ethanol, carrying out vacuum drying on the obtained white solid at 50 ℃ for 12 h to obtain polystyrene microspheres, and introducing the polystyrene microspheres serving as a template into carbon nanotube sponge by using graphene;
Thirdly, preparing the graphene oxide coated polystyrene spheres: dispersing 1-10 g of polystyrene microspheres into 200-500mL of polyethyleneimine aqueous solution (the concentration of PEI is 1-15 mg/mL), and adjusting the pH of a reaction system to 9-12 by using a dilute hydrochloric acid solution and a dilute ammonia solution. And then, carrying out magnetic stirring and ultrasonic dispersion on the reaction system for 0.5-2.5h, carrying out centrifugal separation (8000 rpm for 10 min) on the reaction dispersion, and washing with deionized water for several times (to remove unreacted polyethyleneimine) to obtain the polyethyleneimine-coated polystyrene microsphere. And then dispersing the surface functionalized polystyrene microspheres into 200-500mL of deionized water, adjusting the pH of the dispersion to 9-12, and carrying out ultrasonic treatment for 10 min. Slowly dropwise adding the prepared graphene oxide aqueous solution into the dispersion liquid, gradually clarifying the reaction dispersion liquid along with the gradual addition of the graphene oxide solution, and centrifugally washing the obtained solid to obtain the graphene oxide-coated polystyrene microspheres;
Fourthly, preparing graphene oxide/polystyrene spheres/carbon nanotube sponge: dispersing the graphene-coated polystyrene spheres prepared in the third step into an aqueous solution to prepare 5-100mg/ml, pouring the solution into the carbon nanotube sponge prepared in the first step by using a vacuum pouring method, and finally preparing a graphene/polystyrene sphere/carbon nanotube sponge material by using a freeze drying method;
Fifthly, preparing the graphene-carbon nanotube hybrid sponge: and (3) heating the oxidized graphene/polystyrene spheres/carbon nanotube sponge in the fourth step by adopting a heat treatment method (at the temperature of 300-1200 ℃), removing the polystyrene spheres, and reducing the oxidized graphene to obtain the high-performance graphene-carbon nanotube hybrid sponge.
the invention also discloses graphene-carbon nanotube hybrid sponge, and the carbon nanotube hybrid sponge contains graphene. Further, the compound is prepared by any one of the preparation methods.
compared with the prior art, the invention has the beneficial effects that:
By adopting the technical scheme of the invention, the graphene is mixed in the carbon nano tubes which are mutually overlapped, wound and supported to be assembled into the three-dimensional net structure, so that the steric hindrance effect between the carbon nano tubes in the carbon nano tube sponge is solved, and the problem that the graphene cannot be successfully introduced into the carbon nano tube sponge by the existing method is solved. Meanwhile, the excellent performance of the carbon nanotube sponge is kept, and the conductivity of the carbon nanotube sponge is enhanced. The density of the obtained graphene-carbon nano tube hybrid sponge is only 3-20 mg/cm3Due to the carbon nanotubes themselvesthe structure is staggered with the graphene, the graphene has good compression performance, and the graphene can still completely recover the original shape under the condition that the compression rate is 90%; meanwhile, the graphene-carbon nanotube hybrid sponge prepared by the embodiment has a high specific surface area of 40m2/g -115m2(ii)/g; the high conductivity is 130-180S/m, the mechanical and electrical properties are excellent, no attenuation can be caused under 2000 compression cycles, and the high conductivity type piezoelectric ceramic material is expected to be applied to mechanical and electrical sensors. Meanwhile, the electromagnetic shielding material has excellent electromagnetic shielding performance.
according to a brand new preparation concept, the carbon nanotube sponge is used as a precursor, the graphene-carbon nanotube hybrid sponge is prepared by adopting a vacuum infusion method, and the graphene is introduced into the carbon nanotube sponge, so that the specific surface area of the reinforcement is increased, the conductivity of the carbon nanotube sponge is improved, and the electromagnetic shielding effect of the carbon nanotube sponge is improved.
Drawings
fig. 1 is a schematic diagram of the preparation of the graphene-carbon nanotube hybrid sponge of the present invention.
fig. 2 is a morphology diagram of the graphene-carbon nanotube hybrid sponge obtained in example 2 of the present invention.
Fig. 3 is an SEM photograph of the graphene-carbon nanotube hybrid sponge obtained in example 2 of the present invention.
Fig. 4 is a mechanical cycle performance diagram of the graphene-carbon nanotube hybrid sponge obtained in example 2 of the present invention.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
As shown in fig. 1, a graphene-carbon nanotube hybrid sponge is prepared by the following steps:
Step one, preparing the carbon nanotube sponge, namely preparing the carbon nanotube sponge by adopting a chemical vapor deposition method:
Ultrasonically dissolving a catalyst ferrocene in a liquid carbon source 1, 2-dichlorobenzene to obtain a catalyst/carbon source solution, and preparing 5-30g of ferrocene powder in every 90-300ml of 1, 2-dichlorobenzene in a ratio; injecting the catalyst/carbon source solution into a preheating zone of the tubular furnace by using a precise injection pump for rapid vaporization, and carrying the carbon source and the catalyst into a reaction zone of the tubular furnace by using H2/Ar carrier gas for generation, growth and stacking to form carbon nanotube sponge;
Wherein the temperature of the preheating zone is 180-450 ℃, and the temperature of the high-temperature reaction zone is 700-1200 ℃.
Step two, preparing Polystyrene (PS) balls:
Firstly, 0.1-10 g of polyvinylpyrrolidone (PVP) and ethanol-water mixed solvent (100-500 g of ethanol and 5-100 g of deionized water) are added into a three-necked bottle, magnetic stirring is carried out until PVP solid is completely dissolved, and nitrogen is introduced to exhaust air in the bottle. Dissolving 0.1-5g of Azodiisobutyronitrile (AIBN) in 1-100 g of styrene monomer, slowly dripping into a reaction system, heating to 60-80 ℃ under the protection of nitrogen and at a certain stirring speed, and carrying out polymerization reaction for 5-48 h to obtain a polystyrene emulsion sample. And after the reaction system is cooled to room temperature, carrying out centrifugal treatment on the emulsion sample (1000-9000 rpm, 1-30 min), washing the emulsion sample for 1-10 times by using ethanol, and carrying out vacuum drying on the obtained white solid at 50 ℃ for 12 h to obtain the polystyrene microspheres which are used as templates for introducing graphene.
Step three, preparing the graphene oxide coated polystyrene microspheres:
Dispersing 1-10 g of polystyrene microspheres into 200-500mL of polyethyleneimine aqueous solution (the concentration of PEI is 5-15 mg/mL), and adjusting the pH of a reaction system to 9-12 by using a dilute hydrochloric acid solution and a dilute ammonia solution. And then, carrying out magnetic stirring and ultrasonic dispersion on the reaction system for 0.5-2.5h, carrying out centrifugal separation (8000 rpm for 10 min) on the reaction dispersion, and washing with deionized water for several times (to remove unreacted polyethyleneimine) to obtain the polyethyleneimine-coated polystyrene microsphere. And then dispersing the surface functionalized polystyrene microspheres into 200-500mL of deionized water, adjusting the pH of the dispersion to 9-12, and carrying out ultrasonic treatment for 10 min. Slowly dropwise adding the prepared graphene oxide aqueous solution into the dispersion liquid, gradually clarifying the reaction dispersion liquid along with the gradual addition of the graphene oxide solution, and centrifugally washing the obtained solid to obtain the graphene oxide-coated polystyrene microsphere.
Step four, preparing graphene oxide/polystyrene microsphere/carbon nanotube sponge:
Dispersing the graphene oxide-coated polystyrene microspheres prepared in the third step into an aqueous solution to prepare 5-100mg/ml, pouring the solution into the carbon nanotube sponge prepared in the first step by using a vacuum pouring method, and finally preparing a graphene/polystyrene microsphere/carbon nanotube sponge material by using a freeze drying method; wherein the vacuum degree of the vacuum oven is-0.1 to 0.5 Mpa.
Step five, preparing the graphene-carbon nanotube hybrid sponge:
And (3) heating the graphene oxide/polystyrene microsphere/carbon nanotube sponge in the fourth step by adopting a heat treatment method (at the temperature of 300-1200 ℃), allowing the polystyrene microsphere to disappear, reducing the graphene oxide, and finally obtaining the high-performance graphene-carbon nanotube hybrid sponge.
further, in the first step, the temperature of the preheating zone is 200-450 ℃, and the temperature of the high-temperature reaction zone is 800-1200 ℃.
Further, the ethanol-water mixed solvent in the step two is obtained by mixing 100-500 g of ethanol and 60-80 g of deionized water.
Further, in the third step, 0.1-10 g of polystyrene microspheres are dispersed into 200-400 mL of polyethyleneimine aqueous solution (the concentration of PEI is 5-10 mg/mL).
Furthermore, the vacuum degree of the vacuum oven in the fourth step is-0.2 to-0.8 Mpa.
And the heat treatment temperature of the graphene-carbon nanotube sponge in the fifth step is 300-800 ℃.
the graphene-carbon nanotube sponge prepared by the simple method has stronger mechanical properties and higher application value than graphene sponge; the prepared graphene-carbon nanotube sponge has high electrical property and good compression property, and has a higher specific surface area than a carbon nanotube, so that the graphene-carbon nanotube sponge-based composite material reinforcement is realized. In addition, the graphene-carbon nanotube sponge with different performance indexes can be obtained by adjusting and controlling the preparation parameters such as the concentration of the graphene/polystyrene microspheres and the heat treatment temperature.
The use is illustrated by specific examples.
Example 1
The graphene-carbon nanotube hybrid sponge is prepared by the following steps:
Step one, preparing carbon nanotube sponge:
Preparing the carbon nanotube sponge by adopting a chemical vapor deposition method: ultrasonically dissolving a catalyst ferrocene in a liquid carbon source 1, 2-dichlorobenzene to obtain a catalyst/carbon source solution, and preparing 5-30g of ferrocene powder in every 90-300ml of 1, 2-dichlorobenzene in a ratio; the catalyst/carbon source solution is injected into the preheating zone of the tube furnace by a precise injection pump to be quickly vaporized, H2Carrying a carbon source and a catalyst into a reaction zone of the tubular furnace by using/Ar carrier gas to generate, grow and stack carbon nanotube sponge; wherein the temperature of the preheating zone is 200 ℃, and the temperature of the reaction zone is 800 ℃.
Step two, preparing Polystyrene (PS) balls:
firstly, 0.1-10 g of polyvinylpyrrolidone (PVP) and ethanol-water mixed solvent (100-500 g of ethanol and 5-100 g of deionized water) are added into a three-necked bottle, magnetic stirring is carried out until PVP solid is completely dissolved, and nitrogen is introduced to exhaust air in the bottle. Dissolving 0.1-5g of Azodiisobutyronitrile (AIBN) in 1-100 g of styrene monomer, slowly dripping into a reaction system, heating to 60-80 ℃ under the protection of nitrogen and at a certain stirring speed, and carrying out polymerization reaction for 5-48 h to obtain a polystyrene emulsion sample. And after the reaction system is cooled to room temperature, carrying out centrifugal treatment on the emulsion sample (1000-9000 rpm, 1-30 min), washing the emulsion sample for 1-10 times by using ethanol, and carrying out vacuum drying on the obtained white solid at 50 ℃ for 12 h to obtain the polystyrene microspheres which are used as templates for introducing graphene.
Step three, preparing the graphene oxide coated polystyrene microspheres:
Dispersing 1-10 g of polystyrene microspheres into 200-500mL of polyethyleneimine aqueous solution (the concentration of PEI is 5-15 mg/mL), and adjusting the pH of a reaction system to 9-12 by using a dilute hydrochloric acid solution and a dilute ammonia solution. And then, carrying out magnetic stirring and ultrasonic dispersion on the reaction system for 0.5-2.5h, carrying out centrifugal separation (8000 rpm for 10 min) on the reaction dispersion, and washing with deionized water for several times (to remove unreacted polyethyleneimine) to obtain the polyethyleneimine-coated polystyrene microsphere. And then dispersing the surface functionalized polystyrene microspheres into 200-500mL of deionized water, adjusting the pH of the dispersion to 9-12, and carrying out ultrasonic treatment for 10 min. Slowly dropwise adding the prepared graphene oxide aqueous solution into the dispersion liquid, gradually clarifying the reaction dispersion liquid along with the gradual addition of the graphene oxide solution, and centrifugally washing the obtained solid to obtain the graphene oxide-coated polystyrene microsphere.
Step four, preparing graphene/polystyrene microsphere/carbon nanotube sponge:
dispersing the graphene-coated polystyrene microspheres prepared in the third step into an aqueous solution to prepare 5-100mg/ml, pouring the solution into the carbon nanotube sponge prepared in the first step by using a vacuum pouring method, and finally preparing a graphene oxide/polystyrene microspheres/carbon nanotube sponge material by using a freeze drying method; the vacuum degree of the vacuum perfusion is-0.1 to-0.5 Mpa.
step five, preparing the graphene-carbon nanotube hybrid sponge:
And (3) heating the oxidized graphene/polystyrene microsphere/carbon nanotube sponge in the fourth step by adopting a heat treatment method at the temperature of 300 ℃ to obtain the high-performance graphene-carbon nanotube hybrid sponge.
the density of the graphene-carbon nanotube hybrid sponge obtained in the embodiment is 15mg/cm3Compared with other sponge materials, the graphene-carbon nanotube hybrid sponge has the characteristic of being lighter, is of a three-dimensional network structure, can still completely recover under the condition that the compression rate is 90%, and shows good compression performance; meanwhile, the graphene-carbon nanotube hybrid sponge prepared by the embodiment has a high specific surface area, and the specific surface area is increased to 90.5m2(ii) in terms of/g. The conductivity is 170S/m, and the high conductivity has better application prospect in the force electric sensor.
Example 2
The graphene-carbon nanotube hybrid sponge is prepared by the following steps:
step one, preparing carbon nanotube sponge: preparing the carbon nanotube sponge by adopting a chemical vapor deposition method: ultrasonically dissolving a catalyst ferrocene in a liquid carbon source 1, 2-dichlorobenzene to obtain a catalyst/carbon source solution, and preparing 5-30g of ferrocene powder in every 90-300ml of 1, 2-dichlorobenzene in a ratio; injecting the catalyst/carbon source solution into a preheating zone of the tubular furnace by using a precise injection pump for rapid vaporization, and carrying the carbon source and the catalyst into a reaction zone of the tubular furnace by using H2/Ar carrier gas for generation, growth and stacking to form carbon nanotube sponge; wherein the temperature of the preheating zone is 180-400 ℃, and the temperature of the reaction zone is 700-1000 ℃.
Step two, preparing Polystyrene (PS) balls:
firstly, 0.1-10 g of polyvinylpyrrolidone (PVP) and ethanol-water mixed solvent (100-500 g of ethanol and 5-100 g of deionized water) are added into a three-necked bottle, magnetic stirring is carried out until PVP solid is completely dissolved, and nitrogen is introduced to exhaust air in the bottle. Dissolving 0.1-5g of Azodiisobutyronitrile (AIBN) in 1-100 g of styrene monomer, slowly dripping into a reaction system, heating to 60-80 ℃ under the protection of nitrogen and at a certain stirring speed, and carrying out polymerization reaction for 5-48 h to obtain a polystyrene emulsion sample. And after the reaction system is cooled to room temperature, carrying out centrifugal treatment on the emulsion sample (1000-9000 rpm, 1-30 min), washing the emulsion sample for 1-10 times by using ethanol, and carrying out vacuum drying on the obtained white solid at 50 ℃ for 12 h to obtain the polystyrene microspheres, wherein the polystyrene microspheres are used as templates of the graphene hollow microspheres.
step three, preparing the polystyrene microspheres coated with the graphene:
Dispersing 1-10 g of polystyrene microspheres into 200-500mL of polyethyleneimine aqueous solution (the concentration of PEI is 5-15 mg/mL), and adjusting the pH of a reaction system to 9-11 by using a dilute hydrochloric acid solution and a dilute ammonia solution. And then, carrying out magnetic stirring and ultrasonic dispersion on the reaction system for 0.5-2.5h, carrying out centrifugal separation (8000 rpm for 10 min) on the reaction dispersion, and washing with deionized water for several times (to remove unreacted polyethyleneimine) to obtain the polyethyleneimine-coated polystyrene microsphere. And then dispersing the surface functionalized polystyrene microspheres into 200-500mL of deionized water, adjusting the pH of the dispersion to 9-11, and carrying out ultrasonic treatment for 10 min. Slowly dropwise adding the prepared graphene oxide aqueous solution into the dispersion liquid, gradually clarifying the reaction dispersion liquid along with the gradual addition of the graphene oxide solution, and centrifugally washing the obtained solid to obtain the graphene oxide-coated polystyrene microsphere.
Step four, preparing graphene/polystyrene microsphere/carbon nanotube sponge:
Dispersing the graphene-coated polystyrene microspheres prepared in the third step into an aqueous solution to prepare 5-100mg/ml, pouring the solution into the carbon nanotube sponge prepared in the first step by using a vacuum pouring method, and finally preparing a graphene/polystyrene microsphere/carbon nanotube sponge material by using a freeze drying method; the vacuum degree of the vacuum perfusion is-0.1 to-0.5 Mpa.
Step five, preparing the graphene-carbon nanotube hybrid sponge:
and (3) heating the graphene/polystyrene microsphere/carbon nanotube sponge in the fourth step by adopting a heat treatment method, wherein the temperature is 300-800 ℃, and obtaining the high-performance graphene-carbon nanotube hybrid sponge.
Fig. 2 is a diagram of a sample of the graphene-carbon nanotube hybrid sponge obtained in example 2, from which it can be seen that the graphene-carbon nanotube has a flat surface and contains pores; fig. 3 is an SEM photograph of the graphene-carbon nanotubes obtained in example 2, from which it can be seen that graphene has been introduced into a carbon nanotube sponge; fig. 4 is a mechanical cycle photograph of the graphene-carbon nanotube obtained in example 2, and it can be seen that the graphene-carbon nanotube has good compressive cycle performance.
the density of the graphene-carbon nanotube hybrid sponge obtained in the embodiment is 7mg/cm3Compared with other sponge materials, the graphene-carbon nanotube hybrid sponge has the characteristic of being lighter, is of a three-dimensional network structure, can still completely recover under the condition that the compression rate is 90%, and shows good compression performance; meanwhile, the graphene-carbon nanotube hybrid sponge prepared by the embodiment has higher specific surface arearise to 60m2(ii) in terms of/g. The conductivity is 130S/m, and the high conductivity has better application prospect in the force electric sensor.
Example 3
The graphene-carbon nanotube hybrid sponge is prepared by the following steps:
Step one, preparing carbon nanotube sponge:
Preparing the carbon nanotube sponge by adopting a chemical vapor deposition method: ultrasonically dissolving a catalyst ferrocene in a liquid carbon source 1, 2-dichlorobenzene to obtain a catalyst/carbon source solution, and preparing 5-30g of ferrocene powder in every 90-300ml of 1, 2-dichlorobenzene in a ratio; the catalyst/carbon source solution is injected into the preheating zone of the tube furnace by a precise injection pump to be quickly vaporized, H2carrying a carbon source and a catalyst into a reaction zone of the tubular furnace by using/Ar carrier gas to generate, grow and stack carbon nanotube sponge;
wherein the temperature of the preheating zone is 180-400 ℃, and the temperature of the reaction zone is 700-1000 ℃.
Step two, preparing Polystyrene (PS) balls:
Firstly, 0.1-10 g of polyvinylpyrrolidone (PVP) and ethanol-water mixed solvent (100-500 g of ethanol and 5-100 g of deionized water) are added into a three-necked bottle, magnetic stirring is carried out until PVP solid is completely dissolved, and nitrogen is introduced to exhaust air in the bottle. Dissolving 0.1-5g of Azodiisobutyronitrile (AIBN) in 1-100 g of styrene monomer, slowly dripping into a reaction system, heating to 60-80 ℃ under the protection of nitrogen and at a certain stirring speed, and carrying out polymerization reaction for 5-48 h to obtain a polystyrene emulsion sample. And after the reaction system is cooled to room temperature, carrying out centrifugal treatment on the emulsion sample (1000-9000 rpm, 1-30 min), washing the emulsion sample for 1-10 times by using ethanol, and carrying out vacuum drying on the obtained white solid at 50 ℃ for 12 h to obtain the polystyrene microspheres, wherein the polystyrene microspheres are used as templates of the graphene hollow microspheres.
Step three, preparing the polystyrene microspheres coated with the graphene:
dispersing 1-10 g of polystyrene microspheres into 200-500mL of polyethyleneimine aqueous solution (the concentration of PEI is 5-15 mg/mL), and adjusting the pH of a reaction system to 9-11 by using a dilute hydrochloric acid solution and a dilute ammonia solution. And then, carrying out magnetic stirring and ultrasonic dispersion on the reaction system for 0.5-2.5h, carrying out centrifugal separation (8000 rpm for 10 min) on the reaction dispersion, and washing with deionized water for several times (to remove unreacted polyethyleneimine) to obtain the polyethyleneimine-coated polystyrene microsphere. And then dispersing the surface functionalized polystyrene microspheres into 200-500mL of deionized water, adjusting the pH of the dispersion to 9-11, and carrying out ultrasonic treatment for 10 min. Slowly dropwise adding the prepared graphene oxide aqueous solution into the dispersion liquid, gradually clarifying the reaction dispersion liquid along with the gradual addition of the graphene oxide solution, and centrifugally washing the obtained solid to obtain the graphene oxide-coated polystyrene microsphere.
Step four, preparing graphene oxide/polystyrene microsphere/carbon nanotube sponge:
Dispersing the graphene-coated polystyrene microspheres prepared in the third step into an aqueous solution to prepare 5-100mg/ml, pouring the solution into the carbon nanotube sponge prepared in the first step by using a vacuum pouring method, and finally preparing a graphene oxide/polystyrene microspheres/carbon nanotube sponge material by using a freeze drying method; the vacuum degree of the vacuum perfusion is-0.1 to-0.5 Mpa.
Step five, preparing the graphene-carbon nanotube hybrid sponge: and (3) heating the graphene/polystyrene microsphere/carbon nanotube sponge in the fourth step by using a heat treatment method, wherein the temperature is 300-800 ℃, and obtaining the high-performance graphene-carbon nanotube hybrid sponge.
the density of the graphene-carbon nanotube hybrid sponge obtained in the embodiment is 8mg/cm3Compared with other sponge materials, the graphene-carbon nanotube hybrid sponge has the characteristic of being lighter, is of a three-dimensional network structure, can still completely recover under the condition that the compression rate is 90%, and shows good compression performance; meanwhile, the graphene-carbon nanotube hybrid sponge prepared by the embodiment has a high specific surface area, and the specific surface area is increased to 80m2(ii) in terms of/g. The conductivity is 150S/m, and the high conductivity has better application prospect in the force electric sensor.
example 4
the graphene-carbon nanotube hybrid sponge is prepared by the following steps:
step one, preparing carbon nanotube sponge: preparing the carbon nanotube sponge by adopting a chemical vapor deposition method: ultrasonically dissolving a catalyst ferrocene in a liquid carbon source 1, 2-dichlorobenzene to obtain a catalyst/carbon source solution, and preparing 5-30g of ferrocene powder in every 90-300ml of 1, 2-dichlorobenzene in a ratio; injecting the catalyst/carbon source solution into a preheating zone of the tubular furnace by using a precise injection pump for rapid vaporization, and carrying the carbon source and the catalyst into a reaction zone of the tubular furnace by using H2/Ar carrier gas for generation, growth and stacking to form carbon nanotube sponge; wherein the temperature of the preheating zone is 180-400 ℃, and the temperature of the reaction zone is 700-1000 ℃.
Step two, preparing Polystyrene (PS) balls:
Firstly, 0.1-10 g of polyvinylpyrrolidone (PVP) and ethanol-water mixed solvent (100-500 g of ethanol and 5-100 g of deionized water) are added into a three-necked bottle, magnetic stirring is carried out until PVP solid is completely dissolved, and nitrogen is introduced to exhaust air in the bottle. Dissolving 0.1-5g of Azodiisobutyronitrile (AIBN) in 1-100 g of styrene monomer, slowly dripping into a reaction system, heating to 60-80 ℃ under the protection of nitrogen and at a certain stirring speed, and carrying out polymerization reaction for 5-48 h to obtain a polystyrene emulsion sample. And after the reaction system is cooled to room temperature, carrying out centrifugal treatment on the emulsion sample (1000-9000 rpm, 1-30 min), washing the emulsion sample for 1-10 times by using ethanol, and carrying out vacuum drying on the obtained white solid at 50 ℃ for 12 h to obtain the polystyrene microspheres which are used as templates for introducing graphene.
Step three, preparing the graphene oxide coated polystyrene microspheres:
Dispersing 1-10 g of polystyrene microspheres into 200-500mL of polyethyleneimine aqueous solution (the concentration of PEI is 5-15 mg/mL), and adjusting the pH of a reaction system to 9-12 by using a dilute hydrochloric acid solution and a dilute ammonia solution. And then, carrying out magnetic stirring and ultrasonic dispersion on the reaction system for 0.5-2.5h, carrying out centrifugal separation (8000 rpm for 10 min) on the reaction dispersion, and washing with deionized water for several times (to remove unreacted polyethyleneimine) to obtain the polyethyleneimine-coated polystyrene microsphere. And then dispersing the surface functionalized polystyrene microspheres into 200-500mL of deionized water, adjusting the pH of the dispersion to 9-11, and carrying out ultrasonic treatment for 10 min. Slowly dropwise adding the prepared graphene oxide aqueous solution into the dispersion liquid, gradually clarifying the reaction dispersion liquid along with the gradual addition of the graphene oxide solution, and centrifugally washing the obtained solid to obtain the graphene oxide-coated polystyrene microsphere.
Step four, preparing graphene oxide/polystyrene microsphere/carbon nanotube sponge:
dispersing the graphene-coated polystyrene microspheres prepared in the third step into an aqueous solution to prepare 5-100mg/ml, pouring the solution into the carbon nanotube sponge prepared in the first step by using a vacuum pouring method, and finally preparing a graphene oxide/polystyrene microspheres/carbon nanotube sponge material by using a freeze drying method; the vacuum degree of the vacuum perfusion is-0.1 to-0.5 Mpa.
step five, preparing the graphene-carbon nanotube hybrid sponge:
And (3) heating the graphene/polystyrene microsphere/carbon nanotube sponge in the fourth step by adopting a heat treatment method, wherein the temperature is 300-1200 ℃, and obtaining the high-performance graphene-carbon nanotube hybrid sponge.
The density of the graphene-carbon nanotube hybrid sponge obtained in the embodiment is 9.2mg/cm3Compared with other sponge materials, the graphene-carbon nanotube hybrid sponge has the characteristic of being lighter, is of a three-dimensional network structure, can still completely recover under the condition that the compression rate is 90%, and shows good compression performance; meanwhile, the graphene-carbon nanotube hybrid sponge prepared by the embodiment has a high specific surface area, and the specific surface area is increased to 90.2m2(ii) in terms of/g. The conductivity is 161S/m, and the high conductivity has better application prospect in the force electric sensor.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. a preparation method of a graphene-carbon nanotube hybrid sponge is characterized by comprising the following steps:
Step S1, preparing carbon nanotube sponge;
Step S2, preparing polystyrene microspheres;
step S3, preparing graphene oxide coated polystyrene microspheres;
step S4, dispersing the graphene-coated polystyrene microspheres into an aqueous solution, filling the aqueous solution into the carbon nanotube sponge in vacuum, and then obtaining a graphene/polystyrene microsphere/carbon nanotube sponge material by adopting a freeze drying method;
Step S5, heating the obtained graphene/polystyrene microsphere/carbon nanotube sponge material to remove the polystyrene microsphere and reduce the graphene oxide to obtain the graphene-carbon nanotube hybrid sponge.
2. The method of preparing a graphene-carbon nanotube hybrid sponge according to claim 1, wherein: the preparation of the carbon nanotube sponge in the step S1 comprises dissolving catalyst ferrocene in liquid carbon source 1, 2-dichlorobenzene to obtain catalyst/carbon source solution, injecting the catalyst/carbon source solution into a preheating zone of a tube furnace for vaporization, and evaporating H2the/Ar carrier gas brings the carbon source and the catalyst into the reaction zone of the tubular furnace to react to form the carbon nanotube sponge.
3. the method of preparing a graphene-carbon nanotube hybrid sponge according to claim 2, wherein: the proportion of the catalyst/carbon source solution is that 5-30g of ferrocene powder is dissolved in every 90-300ml of 1, 2-dichlorobenzene; the temperature of the preheating zone is 180-450 ℃, and the temperature of the reaction zone is 700-1200 ℃.
4. The method of preparing a graphene-carbon nanotube hybrid sponge according to claim 3, wherein:The temperature of the preheating zone is 200-400 ℃, and the temperature of the reaction zone is 800-1000 ℃; said H2H in/Ar carrier gas2the volume ratio of/Ar is 1:1-1:4, and the flow rate of carrier gas is 400-2000 mL/min.
5. the method for preparing the graphene ~ carbon nanotube hybrid sponge according to claim 2, wherein the step S2 is to prepare the polystyrene microspheres by dissolving an initiator in a styrene monomer, adding the styrene monomer into a polyvinylpyrrolidone solution under an inert gas environment, stirring, heating to 60 ~ 80 ℃ for polymerization reaction for 5 ~ 48 h to obtain a polystyrene emulsion sample, cooling the polystyrene emulsion sample to room temperature, centrifuging, washing, and vacuum ~ drying the obtained white solid at 40 ~ 55 ℃ to obtain the polystyrene microspheres.
6. The method of preparing a graphene-carbon nanotube hybrid sponge according to claim 1, wherein: step S3 includes: dispersing polystyrene microspheres into a polyethyleneimine aqueous solution, adjusting the pH of a reaction system to 9-12, stirring and ultrasonically dispersing for 0.5-2.5h to obtain a reaction dispersion, and performing centrifugal separation and washing on the reaction dispersion to obtain polyethyleneimine-coated polystyrene microspheres;
dispersing the polystyrene microspheres coated with polyethyleneimine into deionized water to obtain a dispersion liquid, adjusting the pH of the dispersion liquid to 9-12, and performing ultrasonic treatment; and dropwise adding the prepared graphene oxide aqueous solution into the dispersion liquid, and then carrying out centrifugal washing to obtain the graphene oxide-coated polystyrene microsphere.
7. the method of preparing a graphene-carbon nanotube hybrid sponge according to claim 6, wherein: the concentration of PEI in the polyethyleneimine aqueous solution is 5-15 mg/mL; the dosage of the polystyrene microspheres and the polyethyleneimine aqueous solution is that each 0.1-10 g of the polystyrene microspheres are dispersed into 200-500mL of the polyethyleneimine aqueous solution.
8. The method of preparing a graphene-carbon nanotube hybrid sponge according to claim 7, wherein: the concentration of the graphene oxide aqueous solution is 0.0001-0.003 mg/ml.
9. the method for preparing the graphene-carbon nanotube hybrid sponge according ~ any one of claims 1 ~ 8, wherein the step S4 comprises the steps of dispersing the prepared graphene oxide-coated polystyrene microspheres into an aqueous solution ~ prepare a suspension of 5-100mg/ml, pouring the suspension into 1-100mg of carbon nanotube sponge by a vacuum pouring method, and finally preparing the graphene oxide/polystyrene spheres/carbon nanotube sponge material by a freeze drying method.
10. The method of preparing a graphene-carbon nanotube hybrid sponge according to claim 9, wherein: the vacuum degree of the vacuum infusion is-0.1 MPa-1 MPa; in step S5, the temperature of the heat treatment is 300 ℃ to 1200 ℃.
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