CN103224227A - Microwave preparation method of graphene sheet and carbon nanotube/graphene sheet composite material - Google Patents
Microwave preparation method of graphene sheet and carbon nanotube/graphene sheet composite material Download PDFInfo
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- CN103224227A CN103224227A CN2012100211569A CN201210021156A CN103224227A CN 103224227 A CN103224227 A CN 103224227A CN 2012100211569 A CN2012100211569 A CN 2012100211569A CN 201210021156 A CN201210021156 A CN 201210021156A CN 103224227 A CN103224227 A CN 103224227A
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Abstract
The invention provides a microwave preparation method of a graphene sheet and a carbon nanotube/graphene sheet composite material through in-situ synthesis, which comprises the following steps: drying and oxidizing or intercalating the graphene sheet, and placing in a microwave reaction chamber; vacuum-pumping the microwave reaction chamber and introducing protective gas, performing microwave heating on the reaction chamber to the temperature of 300-800 DEG C, introducing carbon source gas and protective gas in the reaction chamber, reacting the carbon source gas, performing in-situ growth on the carbon nanotube or carbon nano fiber in the graphene sheet to obtain the products. The microwave preparation method of the composite material employs the microwave heating method, the graphene-based composite material of a carbon nano-material with a one-dimensional structure can be subjected to in-situ preparation, a synthesis technology in advance is not required, the technology is simple, and the production cost is reduced. In addition, a microwave heating technology is employed, the microwave preparation method has the advantages of fast heating speed, high efficiency, less energy consumption, short production period and reduced preparation cost.
Description
Technical field
The present invention relates to the preparation method of nano composite material, relate in particular to the microwave preparation of graphene-based matrix material.Resulting product can be used for a plurality of technical fields, especially the energy storage field.
Background technology
Graphene is a kind of carbonaceous novel material by the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape crystalline network, is the elementary cell that makes up other dimension carbonaceous material (as zero dimension soccerballene, one dimension carbon nanotube, three-dimensional graphite).Graphene has excellent electricity, calorifics, mechanics, chemical property, has potential to use in each side such as the nano-electron in future, electrochemical energy storage, matrix material, conductive additive, transmitters.Graphene/carbon nano tube compound material the two particular performances separately that can be coupled is expected to obtain the novel multifunctional material.
Preparation method of graphene mainly contains mechanically peel method, epitaxial crystal growth method, chemical Vapor deposition process, the expansion of graphite oxide Rapid Thermal and graphene oxide method of reducing etc.Compare additive method, the graphite oxide Rapid Thermal expands and the graphene oxide method of reducing obtains the magnanimity Graphene easily, technology is easy to amplify, but existing graphene oxide chemical reduction method, simultaneously more adopt as poisonous reductive agent contaminate environment such as hydrazine hydrate with influence HUMAN HEALTH.Graphite oxide Rapid Thermal expansion rule needs to carry out under the very high temperature, is unfavorable for energy-conservation.Above several method ubiquity production cycle length, complex process, energy consumption height have limited further fundamental research of Graphene and matrix material thereof and practical application to a certain extent.Therefore, need seek simple, efficient, the low-cost method for preparing graphene film and based composites thereof of a kind of technology.
Summary of the invention
In view of this, need provide a kind of technology is simple, efficient, cost the is low graphene film and the microwave preparation of carbon nanotube/graphene film matrix material.
The microwave preparation of a kind of graphene film and carbon nanotube/graphene film matrix material may further comprise the steps:
Graphite granule behind dry oxidation or the intercalation, and be placed in the microwave reaction chamber;
The microwave reaction chamber is vacuumized and feeds protective gas;
With microwave heating reaction chamber to 300～600 ℃, heating 2～180s closes microwave, and the entire reaction system is cooled to 100 ℃ under nitrogen atmosphere, obtain graphene film;
With microwave heating reaction chamber to 500～1000 ℃, be catalyzer with ferrocene etc., in reaction chamber, feed carbon-source gas and protective gas, make carbon-source gas reaction, growth in situ unidimensional carbon nanotube on Graphene.
In the technique scheme, the microwave preparation of described graphene film and matrix material thereof adopts the method for microwave heating, is peeling off in-situ preparing unidimensional CNT (carbon nano-tube) on the graphene film that obtains with microwave, thereby is making technology simple, reduces production costs.In addition, owing to adopt microwave heating technique, have that rate of heating is fast, efficient, energy consumption is little, with short production cycle, preparation cost further reduces.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is the graphene film of the embodiment of the invention and the microwave preparation schematic flow sheet of carbon nanotube/graphene film matrix material.
Fig. 2 is a used structure of reactor synoptic diagram in the microwave preparation of the graphene film of the embodiment of the invention and carbon nanotube/graphene film matrix material;
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
See also Fig. 1, show the graphene film of the embodiment of the invention and the microwave preparation flow process of carbon nanotube/graphene film matrix material, may further comprise the steps:
S01: the graphite granule behind dry oxidation or the intercalation, and be placed in the microwave reaction chamber;
S02: the microwave reaction chamber is vacuumized and feed protective gas;
S03: usefulness microwave heating reaction chamber to 300～800 ℃, in reaction chamber, feed protective gas, peel off fast and obtain graphene film.
S04: usefulness microwave heating reaction chamber to 500～1000 ℃, continue in reaction chamber, to feed carbon-source gas and protective gas, make the carbon-source gas reaction, carbon nano-tube in situ on the Graphene substrate.
In step S01, containing silicon substrate can provide according to following steps: choose graphite oxide or intercalated graphite and carry out drying.Drying temperature is 80-150 ℃.
Fig. 2 shows the structure of the microwave reactor 10 of present embodiment, and this microwave reactor 10 can be a Reaktionsofen, and a reaction chamber 12 is arranged in it.When microwave reactor 10 work, be loaded with oxidation or intercalated graphite 14 in it.Have the gap between graphene film 14 and the reactor wall, pass through with supplied gas.Microwave reaction chamber 12 has gas inlet 18 and outlet 19.Microwave reaction chamber 12 outer periphery are equipped with microwave heating installation, and with microwave absorbing auxiliary heating body 15, for example attached to outer wall or inwall, present embodiment is arranged at inwall on the chamber wall of reaction chamber 12.Microwave absorbing auxiliary heating body 15 can be the drum with the coaxial setting of tubular housing, or only is provided with corresponding to the wall place, chamber of graphene film 14 is local.Because microwave absorbing auxiliary heating body 15 is arranged at inwall, therefore, graphene film 14 can place microwave absorbing auxiliary heating body 15.Microwave absorbing auxiliary heating body 15 can be the gac heating member, is not limited thereto.When microwave heating installation sends microwave 16 and heats, microwave absorbing auxiliary heating body 15 heats up very fast, the thermal medium that adds as graphene film 14 and the gas that passes through, help making full use of the characteristics of microwave rapid heating, make graphene film 14 and the gas that passes through reaches temperature required quickly.In addition, a temperature-control device 17 can be set also,, be used for control reaction temperature as temperature controller.
Step S02 specifically can comprise following process: microwave reaction chamber 12 is vacuumized, make that absolute pressures are lower than 1kPa in the reaction chamber 12, vacuumize after feeding protective gas again, repeat this process repeatedly (as more than three times); In reaction chamber 12, feed the mobile protective gas again, remove the oxygen that remains in the reaction chamber 12.Wherein, protective gas is nitrogen or rare gas element, and as helium, argon gas etc., present embodiment preferably adopts nitrogen.
Among the step S03, the reaction times is preferably 2 seconds～and 180 seconds, the total flux of protective gas preferably is controlled at 50～100sccm, and (sccm is meant gas flux unit under the normal conditions: the milliliter per minute) in the scope.
Among the step S04, the reaction times is preferably 10 minutes～and 120 minutes, the total flux of carbon-source gas and protective gas preferably is controlled at 50～100sccm, and (sccm is meant gas flux unit under the normal conditions: the milliliter per minute) in the scope.For obtaining preferable pattern, for example diameter of CNT (carbon nano-tube) or length, length-to-diameter ratio in other words, present embodiment more preferably the reaction times be 30 minutes～60 minutes, the total flux of carbon-source gas and protective gas more preferably is controlled in 60～100sccm scope.
Temperature of reaction is preferably 500-1000 ℃, and under this temperature, the size of CNT (carbon nano-tube) is more even, and pattern is also consistent.
Carbon-source gas is the low hydrocarbon gas of pyrolysis temperature, for example methane gas, acetylene or propylene etc., and present embodiment preferably adopts methane gas.Catalyzer is selected organic catalysts such as ferrocene, dicyclopentadienylcobalt.Protective gas is above-mentioned nitrogen or rare gas element, and present embodiment preferably adopts nitrogen.The volume ratio of carbon-source gas and protective gas is preferably 1: 9～and 1: 1.
Above step prepared graphene sheet or carbon nanotube/graphene film matrix material can be widely used in for example can using the used conductive agent of lithium ion battery in the products such as various energy storage and various matrix materials.
In the microwave preparation of graphene film or carbon nanotube/graphene film matrix material, method by microwave heating, with the graphene film is matrix, then in-situ preparing carbon nanotube, do not need in advance synthesis technique (promptly do not need in the picture prior art preparation carbon nanotube mix etc.) with graphene film, thereby make technology simple, and can improve the bonding force of the two, reduce production costs.In addition, owing to adopt microwave heating technique, have that rate of heating is fast, efficient, energy consumption is little, with short production cycle, preparation cost further reduces.
In addition, microwave has the non-thermal effect of fast characteristics of spontaneous heating and rate of heating and microwave to the activation of substance reaction and the inducibility of process change, reduced activation energy, changed reaction kinetics, thereby optionally promote reaction and improve the orientation response activity, be easy to matrix surface gas-phase grown nanometer carbon nanotube.
Below be the microwave preparation specific examples of graphene film and carbon nanotube/graphene film based composites, to describe the concrete operations technology of this method in detail.
Embodiment 1
The preparation method of the graphene film of present embodiment and graphene film based composites comprises following concrete steps:
1) present embodiment is chosen the graphite oxide particle of 100g, dries in 100 ℃ of baking ovens.
2) dried graphene oxide particle is placed reaction chamber, vacuumize and make that absolute pressure is lower than 1kPa in the burner hearth, logical nitrogen vacuumizes to normal pressure again, repeats this process three times.Open before the microwave and feed flowing nitrogen earlier in the reaction chamber, remain in oxygen in the reaction chamber with removal.
3) open the gas flow bottle valve, feeding flow is the nitrogen of 100sccm.Use the microwave heating reaction chamber, when temperature rises to 500 ℃ of temperature of reaction fast, behind the 30s to be stripped, close microwave, the entire reaction system is cooled to 100 ℃ under nitrogen atmosphere.
4) using the microwave heating reaction chamber, when temperature rises to 800 ℃ of temperature of reaction fast, open the gas flow bottle valve, is to feed methane gas and nitrogen at 1: 4 according to volume ratio, and total flux is 150sccm.Behind the question response 30min, close microwave and methane gas, the entire reaction system is cooled to room temperature under nitrogen atmosphere.
Embodiment 2
The preparation method of the graphene film of present embodiment and graphene film based composites comprises following concrete steps:
1) present embodiment is chosen the graphite oxide particle of 200g, dries in 100 ℃ of baking ovens.
2) dried graphene oxide particle is placed reaction chamber, vacuumize and make that absolute pressure is lower than 1kPa in the burner hearth, logical nitrogen vacuumizes to normal pressure again, repeats this process three times.Open microwave and go to and feed flowing nitrogen in the reaction chamber earlier, remain in oxygen in the reaction chamber with removal.
3) open the gas flow bottle valve, feeding flow is the nitrogen of 100sccm.Use the microwave heating reaction chamber, when temperature rises to 300 ℃ of temperature of reaction fast, behind the 60s to be stripped, close microwave, the entire reaction system is cooled to 100 ℃ under nitrogen atmosphere.
4) using the microwave heating reaction chamber, when temperature rises to 600 ℃ of temperature of reaction fast, open the gas flow bottle valve, is to feed methane gas and nitrogen at 1: 4 according to volume ratio, and total flux is 200sccm.Behind the question response 60min, close microwave and methane gas, the entire reaction system is cooled to room temperature under nitrogen atmosphere.
Claims (6)
1. the microwave preparation of an original position synthesizing graphite alkene sheet and carbon nanotube/graphene film matrix material may further comprise the steps:
Graphite granule behind dry oxidation or the intercalation, and be placed in the microwave reaction chamber;
The microwave reaction chamber is vacuumized and feeds protective gas;
With microwave heating reaction chamber to 300～600 ℃, heating 2～180s closes microwave, and the entire reaction system is cooled to 100 ℃ under nitrogen atmosphere, obtain graphene film;
With microwave heating reaction chamber to 500～1000 ℃, in reaction chamber, feed carbon-source gas and protective gas, make the carbon-source gas reaction, at the graphene film in-situ growing carbon nano tube.
2. the microwave preparation of carbon nanotube as claimed in claim 1/graphene film matrix material; it is characterized in that; the described carbon-source gas reaction times is 10～60 minutes, and the total flux of described carbon-source gas and protective gas is controlled in 50～100sccm scope.
3. the microwave preparation of carbon nanotube as claimed in claim 1/graphene film matrix material is characterized in that, the volume ratio of described carbon-source gas and protective gas is 1: 9～2: 1.
4. the microwave preparation of carbon nanotube as claimed in claim 1/graphene film matrix material is characterized in that, described protective gas is nitrogen or other rare gas elementes.
5. the microwave preparation of graphene-based matrix material as claimed in claim 1, it is characterized in that, the described step that the microwave reaction chamber was vacuumized and fed protective gas comprises following process: the microwave reaction chamber is vacuumized, make the interior absolute pressure of reaction chamber be lower than 1kPa, vacuumize again after feeding protective gas, repeat this process repeatedly; In reaction chamber, feed the mobile protective gas again, remove the oxygen that remains in the reaction chamber.
6. the microwave preparation of carbon nanotube/graphene film as claimed in claim 1 is characterized in that, described microwave heating reaction chamber to 500～1000 ℃.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104036878A (en) * | 2014-06-24 | 2014-09-10 | 国家纳米科学中心 | Preparation method of graphene-carbon nanotube three-dimensional structure material |
| CN104587930A (en) * | 2014-12-24 | 2015-05-06 | 东南大学 | Synthesis of metal/carbon nanotube composite nanowires and special micro/nano reactor |
| CN105129781A (en) * | 2015-08-10 | 2015-12-09 | 重庆大学 | Preparation method of graphene nanoribbon |
| CN112510204A (en) * | 2021-02-05 | 2021-03-16 | 宁波埃氪新材料科技有限公司 | Carbon nanotube graphene composite conductive agent and preparation method thereof |
| CN113054442A (en) * | 2021-03-11 | 2021-06-29 | 西北工业大学 | Preparation method and superstructure design method of multi-scale three-dimensional graphene-carbon nanotube-nickel-based flexible electromagnetic wave-absorbing composite material |
| CN115849349A (en) * | 2022-12-15 | 2023-03-28 | 上海利物盛纳米科技有限公司 | Method for preparing high-thermal-conductivity graphene heat dissipation film |
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2012
- 2012-01-30 CN CN2012100211569A patent/CN103224227A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104036878A (en) * | 2014-06-24 | 2014-09-10 | 国家纳米科学中心 | Preparation method of graphene-carbon nanotube three-dimensional structure material |
| CN104036878B (en) * | 2014-06-24 | 2018-02-27 | 国家纳米科学中心 | A kind of preparation method of graphene and CNT three-dimensional structure material |
| CN104587930A (en) * | 2014-12-24 | 2015-05-06 | 东南大学 | Synthesis of metal/carbon nanotube composite nanowires and special micro/nano reactor |
| CN104587930B (en) * | 2014-12-24 | 2017-10-27 | 东南大学 | The synthesis of metal/carbon nanotube composite nano-line and special micro-/ nano reactor |
| CN105129781A (en) * | 2015-08-10 | 2015-12-09 | 重庆大学 | Preparation method of graphene nanoribbon |
| CN112510204A (en) * | 2021-02-05 | 2021-03-16 | 宁波埃氪新材料科技有限公司 | Carbon nanotube graphene composite conductive agent and preparation method thereof |
| CN112510204B (en) * | 2021-02-05 | 2021-04-20 | 宁波埃氪新材料科技有限公司 | Carbon nanotube graphene composite conductive agent and preparation method thereof |
| CN113054442A (en) * | 2021-03-11 | 2021-06-29 | 西北工业大学 | Preparation method and superstructure design method of multi-scale three-dimensional graphene-carbon nanotube-nickel-based flexible electromagnetic wave-absorbing composite material |
| CN115849349A (en) * | 2022-12-15 | 2023-03-28 | 上海利物盛纳米科技有限公司 | Method for preparing high-thermal-conductivity graphene heat dissipation film |
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Application publication date: 20130731 |