CN111204741A - Preparation method of three-dimensional graphene/carbon nanotube cross-linked composite material - Google Patents
Preparation method of three-dimensional graphene/carbon nanotube cross-linked composite material Download PDFInfo
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- CN111204741A CN111204741A CN202010043399.7A CN202010043399A CN111204741A CN 111204741 A CN111204741 A CN 111204741A CN 202010043399 A CN202010043399 A CN 202010043399A CN 111204741 A CN111204741 A CN 111204741A
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Abstract
A three-dimensional graphene/carbon nanotube cross-linked composite material and a preparation method thereof belong to the field of functional nano materials. The method comprises the following specific steps: dissolving ferric nitrate nonahydrate and polyvinylpyrrolidone in deionized water to prepare a mixed solution, completely drying and grinding into powder; then placing the powder in a tube furnace to undergo medium-temperature heat treatment in a hydrogen-argon mixed atmosphere to obtain a composite material formed by crosslinking carbon nanotube confinement nano-iron particles and three-dimensional graphene; and then removing the iron nanoparticles through high-temperature heat treatment to obtain the three-dimensional graphene/carbon nanotube cross-linked composite material. The method has the advantages of short production period, low cost, strong repeatability, large-scale preparation, important reference function for preparing the composite material of the graphene and the carbon nano tube, and wide application prospect of the obtained material in the fields of energy storage, catalysis and the like.
Description
Technical Field
The invention belongs to the field of functional nano materials, and particularly relates to a three-dimensional graphene/carbon nano tube cross-linked composite material and a preparation method thereof.
Background
Carbon-based materials are an important traditional material, and have excellent mechanical, optical, electrical, thermal and other properties, so that the carbon-based materials are one of important research directions in the fields of chemistry, materials, physics and the like. And has been widely used in the fields of arc lighting devices, communication devices, electrical equipment, energy storage, electrocatalytic materials, and the like. However, with the development of technology, the performance of the conventional carbon material cannot meet the practical application requirements, and therefore, the development of a novel carbon-based material draws high attention from scientists.
Graphene and carbon nanotubes have been widely studied as star materials in the family of carbon materials in the fields of solar cells, sensors, electrocatalysts, metal ion batteries, and the like because of their very excellent properties. The graphene/carbon nanotube composite material with the three-dimensional cross-linked structure formed by combining the carbon nanotube with the one-dimensional structure and the graphene with the two-dimensional structure can bring the advantages of the two into play and greatly improve the performance. The traditional methods for synthesizing graphene include oxidation-reduction method, chemical vapor deposition method, electrolytic method and the like, but the graphene prepared by the methods is usually low in yield and high in cost; and the application of the graphene sheet in the two-dimensional stacking form in the fields of electrocatalysis, electromagnetic wave absorption materials and the like has limitations. The main preparation method of the carbon nano tube is chemical vapor deposition growth on a catalyst, but the preparation process has higher cost. Although the literature reports (adv. mater.2018,1802011) that the composite material of the carbon nanotube growing on the surface of the graphene is obtained by carrying out heat treatment on the reduced graphene oxide and ZIF-67 compound, the method is complex in process and difficult to prepare in a large scale. Therefore, the three-dimensional graphene/carbon nanotube cross-linked composite material with a specific morphology and a high specific surface area is prepared in a controllable manner in a large scale through a simple process, and has extremely important theoretical and practical significance for the development of the composite material of graphene and carbon nanotubes.
Disclosure of Invention
The invention aims to provide a preparation method for simply, efficiently and massively preparing a three-dimensional graphene/carbon nanotube cross-linked composite material at low cost, so as to solve the problems of complex flow and high cost of the existing preparation method for the graphene/carbon nanotube composite material.
In order to achieve the purpose, the invention adopts the technical scheme that:
a three-dimensional graphene/carbon nanotube crosslinked composite material is characterized in that: the composite material consists of a three-dimensional graphene framework and carbon nanotubes growing in the three-dimensional graphene framework; wherein the carbon nano tube is inserted into the three-dimensional graphene framework and is crosslinked with the three-dimensional graphene.
The preparation method of the three-dimensional graphene/carbon nanotube cross-linked composite material comprises the following steps:
a. dissolving ferric nitrate nonahydrate and polyvinylpyrrolidone in deionized water to prepare a mixed solution, completely drying and grinding into powder;
b. placing the powder in a tube furnace, heating to 150-300 ℃ at a heating rate of 3-6 ℃/min in an argon-hydrogen mixed atmosphere, and preserving heat for 0.5-1.5 h; then heating to 650-800 ℃ at a heating rate of 4-8 ℃/min, and preserving heat for 1-2 h; heating to 850-950 ℃ at the heating rate of 3-6 ℃/min, and preserving heat for 2-3 h; and after the tubular furnace is cooled to room temperature, collecting a black foam product, namely the carbon nano tube confinement nano iron particle and three-dimensional graphene crosslinked composite material.
c. Placing the composite material formed by crosslinking carbon nano tube confinement nano iron particles and three-dimensional graphene in a high-temperature furnace, heating to 2500-3500 ℃ at the heating rate of 4-8 ℃/min in the argon atmosphere, and preserving heat for 3-6 h; and (4) cooling the high-temperature furnace to room temperature, and collecting a product, namely the three-dimensional graphene/carbon nano tube cross-linked composite material.
Further, the mass ratio of ferric nitrate nonahydrate to polyvinylpyrrolidone in the step a is (1.4-1.8): 1.
further, the drying temperature of the mixed solution in the step a is 80 ℃.
Further, the volume ratio of hydrogen to argon in the hydrogen-argon mixed gas in the step b is (2-3): (7-8).
Compared with the prior art, the invention has the beneficial effects that:
1) the composite material is composed of a three-dimensional graphene framework and carbon nanotubes grown in the three-dimensional graphene framework in situ; wherein the carbon nano-tube is inserted into the three-dimensional graphene frame and crosslinked with the three-dimensional graphene to jointly form a three-dimensional conductive network.
2) The preparation method of the composite material is simple and easy to operate, has low cost and can be used for large-scale preparation.
3) The prepared composite material has adjustable graphitization degree and multiple application scenes.
Drawings
Fig. 1 is a scanning electron microscope photograph of the carbon nanotube confinement nano-iron particle/three-dimensional graphene cross-linked composite material prepared in the first embodiment of the present invention, magnified 3000 times.
Fig. 2 is a scanning electron microscope photograph of the carbon nanotube confinement nano-iron particle/three-dimensional graphene cross-linked composite material prepared in the first embodiment of the present invention, which is magnified 4000 times.
Fig. 3 is a scanning electron microscope photograph of 10000 times magnification of the carbon nanotube confinement nano-iron particle/three-dimensional graphene crosslinked composite material prepared in the first embodiment of the present invention.
Fig. 4 is a transmission electron microscope photograph of the carbon nanotube confinement nano-iron particle/three-dimensional graphene cross-linked composite material prepared in the first embodiment of the present invention, magnified 3000 times.
FIG. 5 is a transmission electron micrograph of the carbon nanotube confinement nano-iron particle/three-dimensional graphene crosslinked composite material prepared in the first embodiment of the present invention, which is 6000 times larger
Detailed Description
Example one
Weighing polyvinylpyrrolidone powder and ferric nitrate nonahydrate according to a mass ratio of 1:1.6, dissolving in deionized water to prepare a mixed solution, then placing in a forced air drying oven, keeping the temperature at 80 ℃ until the mixture is completely dried, grinding the dried product into powder, transferring the powder into a crucible, placing the crucible in a tubular furnace, heating to 200 ℃ at a heating rate of 4 ℃/min in an argon-hydrogen mixed gas atmosphere (the volume ratio of hydrogen to argon is 2:8), and keeping the temperature for 0.5 h; then heating to 700 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for 1; heating to 850 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2 h; after the tube furnace is cooled to room temperature, collecting a black foam product which is a composite material formed by crosslinking carbon nano tube confinement nano iron particles and three-dimensional graphene; then placing the carbon nano tube confinement nano iron particle/three-dimensional graphene crosslinked composite material in a high-temperature furnace, heating to 2500 ℃ at the heating rate of 4 ℃/min in the argon atmosphere, and preserving heat for 3 hours; and (4) cooling the high-temperature furnace to room temperature, and collecting a product, namely the three-dimensional graphene/carbon nano tube cross-linked composite material.
Example two
Weighing polyvinylpyrrolidone powder and ferric nitrate nonahydrate according to a mass ratio of 1:1.8, dissolving in deionized water to prepare a mixed solution, then placing in a forced air drying oven, keeping the temperature at 80 ℃ until the mixture is completely dried, grinding the dried product into powder, transferring the powder into a crucible, placing the crucible in a tubular furnace, heating to 200 ℃ at a heating rate of 4 ℃/min in an argon-hydrogen mixed gas atmosphere (the volume ratio of hydrogen to argon is 2:8), and keeping the temperature for 0.5 h; then heating to 700 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for 1; heating to 850 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2 h; after the tube furnace is cooled to room temperature, collecting a black foam product which is a composite material formed by crosslinking carbon nano tube confinement nano iron particles and three-dimensional graphene; then placing the carbon nano tube confinement nano iron particle/three-dimensional graphene crosslinked composite material in a high-temperature furnace, heating to 2500 ℃ at the heating rate of 4 ℃/min in the argon atmosphere, and preserving heat for 3 hours; and (4) cooling the high-temperature furnace to room temperature, and collecting a product, namely the three-dimensional graphene/carbon nano tube cross-linked composite material.
EXAMPLE III
Weighing polyvinylpyrrolidone powder and ferric nitrate nonahydrate according to a mass ratio of 1:1.6, dissolving in deionized water to prepare a mixed solution, then placing in a forced air drying oven, keeping the temperature at 80 ℃ until the mixture is completely dried, grinding the dried product into powder, transferring the powder into a crucible, placing the crucible in a tubular furnace, heating to 250 ℃ at a heating rate of 4 ℃/min in an argon-hydrogen mixed gas atmosphere (the volume ratio of hydrogen to argon is 3:7), and keeping the temperature for 0.5 h; then heating to 700 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for 1; heating to 850 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2 h; after the tube furnace is cooled to room temperature, collecting a black foam product which is a composite material formed by crosslinking carbon nano tube confinement nano iron particles and three-dimensional graphene; then placing the carbon nano tube confinement nano iron particle/three-dimensional graphene crosslinked composite material in a high-temperature furnace, heating to 2800 ℃ at the heating rate of 4 ℃/min in the argon atmosphere, and preserving heat for 3 hours; and (4) cooling the high-temperature furnace to room temperature, and collecting a product, namely the three-dimensional graphene/carbon nano tube cross-linked composite material.
Example four
Weighing polyvinylpyrrolidone powder and ferric nitrate nonahydrate according to a mass ratio of 1:1.8, dissolving in deionized water to prepare a mixed solution, then placing in a forced air drying oven, keeping the temperature at 80 ℃ until the mixture is completely dried, grinding the dried product into powder, transferring the powder into a crucible, placing the crucible in a tubular furnace, heating to 200 ℃ at a heating rate of 4 ℃/min in an argon-hydrogen mixed gas atmosphere (the volume ratio of hydrogen to argon is 3:7), and keeping the temperature for 1 h; then heating to 750 ℃ at the heating rate of 4 ℃/min, and preserving heat for 1; heating to 850 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 2 h; after the tube furnace is cooled to room temperature, collecting a black foam product which is a composite material formed by crosslinking carbon nano tube confinement nano iron particles and three-dimensional graphene; then placing the carbon nano tube confinement nano iron particle/three-dimensional graphene crosslinked composite material in a high-temperature furnace, heating to 3000 ℃ at the heating rate of 4 ℃/min in the argon atmosphere, and preserving heat for 3 hours; and (4) cooling the high-temperature furnace to room temperature, and collecting a product, namely the three-dimensional graphene/carbon nano tube cross-linked composite material.
The above embodiments are only intended to illustrate the technical solution of the present invention and not to limit the same, and it should be understood by those skilled in the art that the specific embodiments of the present invention can be modified or substituted with equivalents with reference to the above embodiments, and any modifications or equivalents without departing from the spirit and scope of the present invention are within the scope of the claims to be appended.
Claims (5)
1. A three-dimensional graphene/carbon nanotube crosslinked composite material is characterized in that: the composite material consists of a three-dimensional graphene framework and carbon nanotubes growing in the three-dimensional graphene framework; wherein the carbon nano tube is inserted into the three-dimensional graphene framework and is crosslinked with the three-dimensional graphene.
2. The preparation method of the three-dimensional graphene/carbon nanotube crosslinked composite material according to claim 1, comprising the steps of:
a. dissolving ferric nitrate nonahydrate and polyvinylpyrrolidone in deionized water to prepare a mixed solution, completely drying and grinding into powder;
b. placing the powder in a tube furnace, heating to 150-300 ℃ at a heating rate of 3-6 ℃/min in an argon-hydrogen mixed atmosphere, and preserving heat for 0.5-1.5 h; then heating to 650-800 ℃ at a heating rate of 4-8 ℃/min, and preserving heat for 1-2 h; heating to 850-950 ℃ at the heating rate of 3-6 ℃/min, and preserving heat for 2-5 h; after the tube furnace is cooled to room temperature, collecting a black foam product, wherein the product is a composite material formed by crosslinking carbon nano tube confinement nano iron particles and three-dimensional graphene;
c. placing the composite material formed by crosslinking carbon nano tube confinement nano iron particles and three-dimensional graphene in a high-temperature furnace, heating to 2500-3500 ℃ at the heating rate of 4-8 ℃/min in the argon atmosphere, and preserving heat for 3-6 h; and (4) cooling the high-temperature furnace to room temperature, and collecting a product, namely the three-dimensional graphene/carbon nano tube cross-linked composite material.
3. The preparation method of the three-dimensional graphene/carbon nanotube crosslinked composite material according to claim 2, wherein the mass ratio of the ferric nitrate nonahydrate to the polyvinylpyrrolidone in the step a is (1.4-1.8): 1.
4. the method for preparing the three-dimensional graphene/carbon nanotube cross-linked composite material according to claim 2, wherein the drying temperature of the mixed solution in the step a is 80 ℃.
5. The preparation method of the three-dimensional graphene/carbon nanotube crosslinked composite material according to claim 2, wherein the volume ratio of hydrogen to argon in the hydrogen-argon mixture gas in the step b is (2-3): (7-8).
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| CN111662688A (en) * | 2020-07-01 | 2020-09-15 | 桂林电子科技大学 | Boron nitride/graphene double-heat-conduction-base aerogel composite phase-change material and preparation method thereof |
| CN111659401A (en) * | 2020-06-30 | 2020-09-15 | 齐鲁工业大学 | Three-dimensional porous carbon nanotube graphene composite membrane and preparation method thereof |
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