CN110562963B - Preparation method of graphene-carbon nanotube hybrid sponge - Google Patents
Preparation method of graphene-carbon nanotube hybrid sponge Download PDFInfo
- Publication number
- CN110562963B CN110562963B CN201910885875.7A CN201910885875A CN110562963B CN 110562963 B CN110562963 B CN 110562963B CN 201910885875 A CN201910885875 A CN 201910885875A CN 110562963 B CN110562963 B CN 110562963B
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- graphene
- sponge
- preparing
- polystyrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
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 the carrier gas is 400-2000 mL/min.
As a further improvement of the present 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 ℃ to perform polymerization reaction for 5-48 h to obtain a polystyrene emulsion sample; and 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 the temperature of 40-55 ℃ to obtain the polystyrene microsphere.
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 rotation 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 the 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 flask, magnetic stirring is carried out until PVP solid is completely dissolved, and nitrogen is introduced to exhaust air in the flask. 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 (1000-9000 rpm for 1-30 min) on the emulsion sample, 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 polystyrene microspheres which are used as templates for introducing graphene into carbon nanotube sponge;
thirdly, preparing the graphene oxide coated polystyrene spheres: 1-10 g of polystyrene microspheres are dispersed in 200-500mL of polyethyleneimine aqueous solution (the concentration of PEI is 1-15 mg/mL), and the pH value of the reaction system is adjusted to 9-12 by using dilute hydrochloric acid solution and 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. Then dispersing the surface functionalized polystyrene microspheres into 200-500mL deionized water, adjusting the pH of the dispersion liquid 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 staggered structure of the carbon nano tube and the graphene and the good compression performance, the original shape can be completely recovered 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 power and electricity performance is excellent, no attenuation can be caused under 2000 compression cycles, and the high conductivity-free piezoelectric ceramic is expected to be applied to a power and electricity sensor. 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 flask, magnetic stirring is carried out until PVP solid is completely dissolved, and nitrogen is introduced to exhaust air in the flask. 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 (1000-9000 rpm for 1-30 min) on the emulsion sample, washing the emulsion sample for 1-10 times by using ethanol, and carrying out vacuum drying on the obtained white solid at the temperature of 50 ℃ for 12 h to obtain the polystyrene microspheres which are used as templates for introducing the graphene.
Step three, preparing the graphene oxide coated polystyrene microspheres:
1-10 g of polystyrene microspheres are dispersed in 200-500mL of polyethyleneimine aqueous solution (the concentration of PEI is 5-15 mg/mL), and the pH value of the reaction system is adjusted to 9-12 by using dilute hydrochloric acid solution and 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. Then dispersing the surface functionalized polystyrene microspheres into 200-500mL deionized water, adjusting the pH of the dispersion liquid 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 second step 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 400 mL of polyethyleneimine aqueous solution with the concentration of PEI being 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 flask, magnetic stirring is carried out until PVP solid is completely dissolved, and nitrogen is introduced to exhaust air in the flask. 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 (1000-9000 rpm for 1-30 min) on the emulsion sample, washing the emulsion sample for 1-10 times by using ethanol, and carrying out vacuum drying on the obtained white solid at the temperature of 50 ℃ for 12 h to obtain the polystyrene microspheres which are used as templates for introducing the graphene.
Step three, preparing the graphene oxide coated polystyrene microspheres:
1-10 g of polystyrene microspheres are dispersed in 200-500mL of polyethyleneimine aqueous solution (the concentration of PEI is 5-15 mg/mL), and the pH value of the reaction system is adjusted to 9-12 by using dilute hydrochloric acid solution and 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. Then dispersing the surface functionalized polystyrene microspheres into 200-500mL deionized water, adjusting the pH of the dispersion liquid 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 flask, magnetic stirring is carried out until PVP solid is completely dissolved, and nitrogen is introduced to exhaust air in the flask. 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 (1000 plus 9000 rpm, 1-30 min) on the emulsion sample, washing 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:
1-10 g of polystyrene microspheres are dispersed in 200-500mL of polyethyleneimine aqueous solution (the concentration of PEI is 5-15 mg/mL), and the pH value of the reaction system is adjusted to 9-11 by using dilute hydrochloric acid solution and 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. Then dispersing the surface functionalized polystyrene microspheres into 200-500mL deionized water, adjusting the pH of the dispersion liquid 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 a high specific surface area, and the specific surface area is increased 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 flask, magnetic stirring is carried out until PVP solid is completely dissolved, and nitrogen is introduced to exhaust air in the flask. 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 (1000 plus 9000 rpm, 1-30 min) on the emulsion sample, washing 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:
1-10 g of polystyrene microspheres are dispersed in 200-500mL of polyethyleneimine aqueous solution (the concentration of PEI is 5-15 mg/mL), and the pH value of the reaction system is adjusted to 9-11 by using dilute hydrochloric acid solution and 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. Then dispersing the surface functionalized polystyrene microspheres into 200-500mL deionized water, adjusting the pH of the dispersion liquid 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 flask, magnetic stirring is carried out until PVP solid is completely dissolved, and nitrogen is introduced to exhaust air in the flask. 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 (1000-9000 rpm for 1-30 min) on the emulsion sample, washing the emulsion sample for 1-10 times by using ethanol, and carrying out vacuum drying on the obtained white solid at the temperature of 50 ℃ for 12 h to obtain the polystyrene microspheres which are used as templates for introducing the graphene.
Step three, preparing the graphene oxide coated polystyrene microspheres:
1-10 g of polystyrene microspheres are dispersed in 200-500mL of polyethyleneimine aqueous solution (the concentration of PEI is 5-15 mg/mL), and the pH value of the reaction system is adjusted to 9-12 by using dilute hydrochloric acid solution and 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. Then dispersing the surface functionalized polystyrene microspheres into 200-500mL deionized water, adjusting the pH of the dispersion liquid 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 (9)
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 oxide coated polystyrene microspheres into an aqueous solution, pouring the aqueous solution into the carbon nanotube sponge in vacuum, and then obtaining a graphene oxide/polystyrene microspheres/carbon nanotube sponge material by adopting a freeze drying method;
step S5, heating the obtained graphene oxide/polystyrene microsphere/carbon nanotube sponge material to remove the polystyrene microsphere and reduce the graphene oxide to obtain graphene-carbon nanotube hybrid sponge;
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.
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 the carrier gas is 400-2000 mL/min.
5. The method of preparing a graphene-carbon nanotube hybrid sponge according to claim 2, wherein: the preparation of the polystyrene microsphere in the step S2 includes: dissolving an initiator in a styrene monomer, adding the initiator into a polyvinylpyrrolidone solution under an inert gas environment, stirring, heating to 60-80 ℃ to perform polymerization reaction for 5-48 h to obtain a polystyrene emulsion sample; and 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 the temperature of 40-55 ℃ to obtain the polystyrene microsphere.
6. The method of preparing a graphene-carbon nanotube hybrid sponge according to claim 1, 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.
7. The method of preparing a graphene-carbon nanotube hybrid sponge according to claim 6, wherein: the concentration of the graphene oxide aqueous solution is 0.0001-0.003 mg/ml.
8. The method for preparing the graphene-carbon nanotube hybrid sponge according to any one of claims 1 to 7, wherein: 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.
9. The method of preparing a graphene-carbon nanotube hybrid sponge according to claim 8, 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 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910885875.7A CN110562963B (en) | 2019-09-19 | 2019-09-19 | Preparation method of graphene-carbon nanotube hybrid sponge |
| AU2020102002A AU2020102002A4 (en) | 2019-09-19 | 2020-08-26 | Preparation method of graphene-carbon nanotube hybrid sponge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910885875.7A CN110562963B (en) | 2019-09-19 | 2019-09-19 | Preparation method of graphene-carbon nanotube hybrid sponge |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110562963A CN110562963A (en) | 2019-12-13 |
| CN110562963B true CN110562963B (en) | 2021-05-18 |
Family
ID=68781178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910885875.7A Active CN110562963B (en) | 2019-09-19 | 2019-09-19 | Preparation method of graphene-carbon nanotube hybrid sponge |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN110562963B (en) |
| AU (1) | AU2020102002A4 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112479182A (en) * | 2020-11-27 | 2021-03-12 | 中宝(西安)科技集团有限公司 | Preparation method of carbon nanotube hollow sphere composite material and composite material |
| CN112827318A (en) * | 2021-02-10 | 2021-05-25 | 中国科学技术大学 | Carbon nanotube sponge low-temperature adsorption plate without adhesive |
| CN112745142B (en) * | 2021-03-04 | 2022-07-19 | 四川大学 | Graphene/calcium phosphate ceramic composite bracket with antibacterial function and preparation method thereof |
| CN113648981A (en) * | 2021-08-12 | 2021-11-16 | 枣庄学院 | Graphene oxide composite microsphere, preparation method thereof and application of graphene oxide composite microsphere in detection of bisphenol compounds |
| CN114177848B (en) * | 2021-12-09 | 2022-08-12 | 四川大学 | Carbon @ iron nano composite material and preparation method thereof |
| CN115014597B (en) * | 2022-04-29 | 2023-09-22 | 深圳大学 | Flexible pressure sensor based on porous structure composite material and preparation method thereof |
| CN115072845A (en) * | 2022-05-17 | 2022-09-20 | 上海电力大学 | Nano porous carbon modified graphite felt cathode material and preparation method and application thereof |
| CN114984892B (en) * | 2022-06-30 | 2023-10-24 | 广东石油化工学院 | Device for producing graphite foamable polystyrene by bulk method |
| CN115322409B (en) * | 2022-08-05 | 2023-10-31 | 镇江立达纤维工业有限责任公司 | Three-dimensional graphene/carbon nano tube/polydimethylsiloxane composite material with efficient sound absorption performance and preparation method thereof |
| CN115282950B (en) * | 2022-08-05 | 2023-05-26 | 西南交通大学 | Preparation method and application of carbon-based hybrid sponge for in-situ catalytic growth |
| CN115739199B (en) * | 2022-11-14 | 2024-07-26 | 上海云松化学有限公司 | Preparation method of oil-soluble graphene modified styrene-divinylbenzene copolymer hydrophobic catalyst carrier |
| CN115819976B (en) * | 2022-12-07 | 2023-06-27 | 山东大学 | Directional arrangement composite smart material and smart sensor using same |
| CN116217312B (en) * | 2023-02-22 | 2024-02-27 | 浙江大学 | Low-migration ferrocenyl functionalized graphene oxide burning rate catalyst and preparation method thereof |
| CN116986588B (en) * | 2023-07-26 | 2024-07-16 | 南方石墨新材料有限公司 | High-strength graphite ball and preparation method thereof |
| CN117398983B (en) * | 2023-10-08 | 2024-04-26 | 北方工业大学 | Preparation method of sponge nickel-based heavy metal chromium ion adsorption material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728329B (en) * | 2012-06-14 | 2014-04-23 | 天津大学 | Porous silica gel used as liquid chromatography stationary phase material and preparation method thereof |
| CN105732036A (en) * | 2016-01-12 | 2016-07-06 | 山东佳星环保科技有限公司 | Method for preparing three-dimensional graphene/carbon nanotube composite material |
| CN107325421A (en) * | 2017-06-22 | 2017-11-07 | 广州中谱检测技术服务有限公司 | A kind of preparation method of polymer/graphene/carbon nano tube compound material |
| CN107739491A (en) * | 2017-11-22 | 2018-02-27 | 陕西盛迈石油有限公司 | A kind of preparation method of graphene/polystyrene conductive composite |
| US10941042B2 (en) * | 2018-04-06 | 2021-03-09 | West Virginia University | Processes and compositions for carbon foams and materials |
| CN109173344A (en) * | 2018-08-31 | 2019-01-11 | 周晓东 | A kind of preparation method of hydrophobicity three-dimensional porous material |
-
2019
- 2019-09-19 CN CN201910885875.7A patent/CN110562963B/en active Active
-
2020
- 2020-08-26 AU AU2020102002A patent/AU2020102002A4/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| AU2020102002A4 (en) | 2020-10-01 |
| CN110562963A (en) | 2019-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110562963B (en) | Preparation method of graphene-carbon nanotube hybrid sponge | |
| CN104961121B (en) | Preparation method for nitrogen-doped nuclear shell hollow carbon | |
| CN107311144A (en) | Preparation method of nitrogen-doped nano porous hollow carbon spheres | |
| CN109346681A (en) | A kind of nuclear shell structure nano silicon-MXene composite negative pole material and preparation method thereof | |
| CN107611394A (en) | A kind of nuclear shell structure nano silicon/graphene composite negative pole of carbon coating and preparation method thereof | |
| CN104671233B (en) | A kind of preparation method of foamy graphite alkene | |
| CN106378093B (en) | Preparation method and application of magnetic hollow graphene-based composite microsphere material | |
| CN103360616A (en) | Method for preparing hybrid film through graphene/nano crystalline cellulose dispersion liquid | |
| CN107188155A (en) | Preparation method of nitrogen-doped nano porous carbon spheres | |
| CN109103443B (en) | Silicon-based negative electrode material and preparation method thereof | |
| CN105460978A (en) | Large-scale preparation method of carbon-doped ferrite porous microspheres | |
| CN109847664B (en) | Conductive thermal expansion type microcapsule and preparation method thereof | |
| CN107046124B (en) | Preparation method of nanoscale silicon cathode of lithium ion battery | |
| CN110283450B (en) | Method for preparing flexible conductive composite material by regulating graphene arrangement through magnetic field | |
| CN113540453B (en) | Internal lithium-philic multi-confinement/induction hollow carbon composite framework of lithium metal cathode and preparation method thereof | |
| WO2016086628A1 (en) | Graphene-polyaniline modified carbon nanotube composite and preparation method therefor | |
| CN108249482B (en) | Magnetic Fe2O3Preparation method of nano particles and method for compounding nano particles with nano carbon material | |
| CN101844759A (en) | Preparation method of controllable hollow carbon nanometer micro ball | |
| CN103146231A (en) | Method for preparing core-shell type carbon nano-tube filling by coating carbon nano-tube through polyionic liquid | |
| Cho et al. | The rise of morphology-engineered microporous organic polymers (ME-MOPs): synthesis and benefits | |
| CN113353917B (en) | Controllable preparation method of self-supporting two-dimensional mesoporous nano material | |
| CN111276684A (en) | Preparation method and application of carbon-coated composite material | |
| CN108047806A (en) | A kind of graphene/Ag- carbon microspheres aeroge coating and its preparation method and application | |
| CN112920001A (en) | Method for preparing nano aluminum/porous copper oxide nano thermite by self-assembly of P4VP | |
| CN112695413A (en) | MXene/porous carbon nanofiber composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |