CN108163842A - A kind of preparation method and application of graphene nano pipe - Google Patents
A kind of preparation method and application of graphene nano pipe Download PDFInfo
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- CN108163842A CN108163842A CN201810064451.XA CN201810064451A CN108163842A CN 108163842 A CN108163842 A CN 108163842A CN 201810064451 A CN201810064451 A CN 201810064451A CN 108163842 A CN108163842 A CN 108163842A
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- graphene
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- graphene oxide
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- C01—INORGANIC CHEMISTRY
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
Abstract
The invention discloses a kind of preparation methods of graphene nano pipe, the described method comprises the following steps：Graphene oxide is placed in ultrasonic disperse in solvent, obtains graphene oxide dispersion, solute is added in and obtains mixed solution, after carrying out electrospinning, pre-oxidation, carbonization under given conditions, is handled using ammonia and finally obtains graphene nano pipe.Graphene nano pipe produced by the present invention has excellent field emission effect performance, and threshold electric field is 0.21V/ μm, and threshold field is 0.42V/ μm, there is larger application value in intelligent switch device is prepared.
Description
Technical field
The present invention relates to technical field of graphene, and in particular to a kind of preparation method and application of graphene nano pipe.
Background technology
Since graphene has a series of unique physicochemical characteristics, such as the mechanical strength of superelevation, high Young mould
Amount, at room temperature excellent electron mobility, very high thermal conductivity, excellent optical absorption characteristic and to the complete of any gas
Full impermeability utilizes transparent from Andre Geim and the Konstantin Novoselov of Univ Manchester UK in 2004
Adhesive tape has received significant attention since being prepared.Its structure type is relatively simple as a kind of flaky material of two dimension for graphene,
But a variety of variations can occur for its macrostructure form, such as two-dimensional film and the macrostructure of three-dimensional, widen graphene
Application field.
Graphite alkenyl nanometer materials are the topological structures of graphene, it greatly remains the same of the intrinsic property of graphene
When, through either physically or chemically preparing new pattern and structure, impart its special performance.
Electrostatic spinning is a kind of novel spining technology, it is sprayed at a high speed based on charged liquid electrolyte in high-voltage electrostatic field
The principle penetrated develops, and core is charged liquid flow deformation in high-voltage electrostatic field, then through melt cooling or it is molten
Agent volatilize and cure, so as to obtain sub-micron even Nano grade fibrous material, with it is at low cost, can large quantities of preparation nanometers
The characteristics of fiber, has been widely used for preparing high polymer nanometer fiber, is the hot spot of Recent study.But there is presently no reports
Continuous, endless graphene nano pipe is directly prepared with electrostatic spinning technique.
Invention content
The purpose of the present invention is to provide a kind of preparation method and application of graphene nano pipe, methods disclosed by the invention
Graphene nanometer sheet that can make dispersion, that shape is irregular makes it be connected with each other by nitrogen-atoms at high temperature, while profit
Continuous graphene nano pipe is become by the use of carbon nano-fiber as template, obtained graphene nano pipe has excellent
Field emission effect, it is of the existing technology to solve the problems, such as available for preparing intelligent switch device.
To achieve the above object, the invention discloses a kind of preparation method of graphene nano pipe, the preparation method packets
Include following steps：
1) graphene oxide is placed in 2~3h of ultrasonic disperse in solvent, obtains graphene oxide dispersion, in graphite oxide
Solute is added in alkene dispersion liquid, and is stirred 24 hours under 65 DEG C of water bath condition, wherein, the quality of graphene oxide and solute
Than being 1/11~1/5, the total mass concentration ranging from 10%~15% of graphene oxide and solute；
2) solution made from step 1) is prepared into nano-composite fiber precursor, electrospinning conditions in electrostatic spinning apparatus
For：Voltage is 25kv, and distance of the syringe needle apart from substrate is 25cm, and solution feed rate is 1ml/h；
3) nano-composite fiber precursor made from step 2) is pre-oxidized 100~120 points at a temperature of 220~240 DEG C
Clock after 950~1050 DEG C are then warming up under inert atmosphere protection, are passed through ammonia and carry out reaction 30~60 minutes, reaction knot
Ammonia is closed after beam and is passed through furnace cooling after inert gas, obtains graphene nano pipe.
Further, the graphene oxide is prepared by micro crystal graphite.
Micro crystal graphite is that its fixation carbon content can reach 99.99% or higher by high temperature purification.Its particle be by
Many tiny crystals are assembled.Therefore the graphene oxide layer being prepared by a conventional method to obtain with the raw material of micro crystal graphite
It is very small, can edge be shifted onto by the gas that reaction generates in the confinement template of carbon nano-fiber and form nanotube.
Further, in step 1), when solvent is n,N-Dimethylformamide or n,N-dimethylacetamide or the two
During arbitrary proportion mixture, the solute is polyacrylonitrile.
Further, in step 1), when solvent is water, the solute is polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl
Any one of base cellulose.
Further, the inert gas is any in nitrogen, argon gas, helium.
To realize above-mentioned another object, prepared by the graphene nano pipe obtained by above-mentioned preparation method disclosed by the invention
Application in intelligent switch device.
The invention has the advantages that：
Preparation process of the present invention is simple, easy to operate, and prepared graphene nano pipe has excellent field emission effect,
Threshold electric field is 0.21V/ μm, and threshold field is 0.42V/ μm, there is larger application value in intelligent switch device is prepared.
Description of the drawings
Fig. 1 is scanning electron microscope (SEM) shape appearance figure of the graphene nano pipe prepared by the present embodiment 1.
Fig. 2 is x-ray photoelectron spectroscopy (XPS) test result figure, wherein, ammonia atmosphere refers to prepared by the present embodiment 1
The x-ray photoelectron spectroscopy figure of graphene nano pipe, argon atmosphere refer to without ammonia processing (other steps with 1 phase of embodiment
The x-ray photoelectron spectroscopy figure of composite nano fiber obtained by together), can obtain from figure, through ammonia handle made from stone
The N element of black alkene nanotube is apparently higher than without the obtained composite nano fiber of ammonia processing, illustrates that N atoms enter graphene
Inside configuration, N atoms by the carbon atom with edge link formed be closed tubular structure.
Fig. 3 is field emission effect performance map (extra electric field and the electric current of the graphene nano pipe prepared by the present embodiment 1
Relation curve).
Fig. 4 is the emission current versus time curve of the graphene nano pipe prepared by the present embodiment 1, can from figure
To see, under fixed current, graphene nano pipe has stable autoelectronic current.
Fig. 5 is the graphene nano pipe of the present invention into pipe process schematic.Carbon/stone is prepared by electrostatic spinning technique
Black alkene nano-composite fiber, then by pre-oxidation, carbonization and ammonia activation processing, you can obtain graphene nano pipe, into
During pipe, the cylindrical structure of carbon nano-fiber plays the role of skeleton and confinement, is passed through during carbonization treatment
Ammonia unbodied carbon is etched, nitrogen-atoms (N) connects the carbon atom of graphene nanometer sheet edge in ammonia, shape
Into graphene nano pipe.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
The preparation method of graphene oxide is as follows in following embodiment：
The concentrated sulfuric acid (the H of 360mL is measured respectively2SO4) and 40mL concentrated phosphoric acid (H3PO4), it adds it to containing microlite
In black 3.0g and mixed-powder containing potassium permanganate 18g.Obtained mixed solution is progressively heated at 50 DEG C in a water bath
And stir 12h.Then it is cooled to room temperature and is poured slowly into the 30% hydrogen peroxide (H containing 3mL2O2) in, pass through
Filter, centrifugation after take out supernatant object, by lower part remaining solid substance continuously with 200mL distilled water, 200mL hydrochloric acid (30%HCl) and
The ethyl alcohol cleaning of 200mL finally dries 48h until neutrality in vacuum drying chamber at a temperature of 60 DEG C.
Embodiment 1
The preparation method of the graphene nano fiber of the present embodiment, includes the following steps：
1) 0.12g graphene oxides are dissolved in 8.8gN, supersound process is carried out in dinethylformamide and obtains oxygen within 2 hours
Graphite alkene dispersion liquid adds in the polyacrylonitrile of 1.08g in above-mentioned graphene oxide dispersion, and in 65 DEG C of water bath condition
Lower stirring 24 hours, wherein, the mass ratio of graphene oxide and polyacrylonitrile is 1/9, graphene oxide and polyacrylonitrile it is total
Mass concentration ranging from 12%；
2) solution made from step 1) is prepared into nano-composite fiber precursor, electrospinning conditions in electrostatic spinning apparatus
For：Voltage is 25kv, and distance of the syringe needle apart from substrate is 25cm, and solution feed rate is 1ml/h；
3) nano-composite fiber precursor made from step 2) is pre-oxidized 120 minutes at a temperature of 220 DEG C, then lazy
Property atmosphere protection under be warming up to 1000 DEG C after, be passed through ammonia and carry out reaction 40 minutes, close ammonia and be passed through lazy after reaction
Furnace cooling after property gas, obtains graphene nano fiber.
Embodiment 2
The preparation method of the graphene nano fiber of the present embodiment, includes the following steps：
1) 0.08g graphene oxides are dissolved in 3.9g water be ultrasonically treated 2 hours and obtain graphene oxide dispersion,
The polyvinyl alcohol of 0.4g is added in above-mentioned graphene oxide dispersion, and is stirred 24 hours under 65 DEG C of water-bath conditional,
Wherein, the mass ratio of graphene oxide and polyvinyl alcohol is 1/5, and the total mass concentration of graphene oxide and polyvinyl alcohol is ranging from
11%；
2) solution made from step 1) is prepared into nano-composite fiber precursor, electrospinning conditions in electrostatic spinning apparatus
For：Voltage is 25kv, and distance of the syringe needle apart from substrate is 25cm, and solution feed rate is 1ml/h；
3) nano-composite fiber precursor prepared by step 2) is pre-oxidized 100 minutes at a temperature of 240 DEG C, then lazy
Property atmosphere protection under be warming up to 950 DEG C after, be passed through ammonia and carry out reaction 60 minutes, close ammonia after reaction and be passed through inertia
Furnace cooling after gas, obtains graphene nano fiber.
Embodiment 3
The preparation method of the graphene nano pipe of the present embodiment, includes the following steps：
1) 0.11g graphene oxides are dissolved in 9g DMAC N,N' dimethyl acetamides be ultrasonically treated 2 hours and are aoxidized
The polyacrylonitrile of 0.89g is added in above-mentioned graphene oxide dispersion by graphene dispersing solution, and the item in 65 DEG C of water-bath
It is stirred 24 hours under part, wherein, the mass ratio of graphene oxide and polyacrylonitrile is 1/8, graphene oxide and polyacrylonitrile
Total mass concentration ranging from 10%；
2) solution made from step 1) is prepared into nano-composite fiber precursor, electrospinning conditions in electrostatic spinning apparatus
For：Voltage is 25kv, and distance of the syringe needle apart from substrate is 25cm, and solution feed rate is 1ml/h；
3) nano-composite fiber precursor prepared by step 2) is pre-oxidized 110 minutes at a temperature of 230 DEG C, then lazy
Property atmosphere protection under be warming up to 1050 DEG C after, be passed through ammonia and carry out reaction 30 minutes, close ammonia and be passed through lazy after reaction
Furnace cooling after property gas, obtains graphene nano pipe.
Embodiment 4
The preparation method of the graphene nano fiber of the present embodiment, includes the following steps：
1) 0.083g graphene oxides are dissolved in 5.8g water be ultrasonically treated and obtain within 2 hours graphene oxide dispersion
The polyvinylpyrrolidone of 0.917g is added in above-mentioned graphene oxide dispersion by liquid, and in 65 DEG C of water-bath conditional
Lower stirring 24 hours, wherein, the mass ratio of graphene oxide and polyacrylonitrile is 1/11, graphene oxide and polyacrylonitrile it is total
Mass concentration ranging from 15%；
2) solution made from step 1) is prepared into nano-composite fiber precursor, electrospinning conditions in electrostatic spinning apparatus
For：Voltage is 25kv, and distance of the syringe needle apart from substrate is 25cm, and solution feed rate is 1ml/h；
3) nano-composite fiber precursor prepared by step 2) is pre-oxidized 120 minutes at a temperature of 225 DEG C, then lazy
Property atmosphere protection under be warming up to 1050 DEG C after, be passed through ammonia and carry out reaction 35 minutes, close ammonia and be passed through lazy after reaction
Furnace cooling after property gas, obtains graphene nano fiber.
Test example
This test example is used to illustrate that graphene nano pipe produced by the present invention has excellent field emission effect.
Field emission effect test condition is：Graphene nano pipe made from embodiment 1 is placed in a spherical confined space,
Spherical airtight container is vacuumized, until vacuum degree is maintained at 10-5Pa.Anode is that the irony of a diameter of 1mm cylinders is visited
Needle, the effective conducting resinl of graphene nano are fixed on the copper step as cathode, and interelectrode distance is 5mm, test
The diode I-V test characterized systematicallies of current-voltage (I-V) characteristic customization.
Test result shows：Its threshold electric field is 0.21V/ μm of (J=10 μ A/cm2), threshold field is 0.42V/ μm of (J=
10mA/cm2)。
Although above having used general explanation and specific embodiment, the present invention is described in detail, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
These modifications or improvements without departing from theon the basis of the spirit of the present invention belong to the scope of protection of present invention.
Claims (6)
1. a kind of preparation method of graphene nano pipe, which is characterized in that the preparation method includes the following steps：
1) graphene oxide is placed in 2~3h of ultrasonic disperse in solvent, obtains graphene oxide dispersion, in graphene oxide point
Solute is added in dispersion liquid, and is stirred 24 hours under 65 DEG C of water bath condition, wherein, the mass ratio of graphene oxide and solute is
1/11~1/5, the total mass concentration ranging from 10%~15% of graphene oxide and solute；
2) solution made from step 1) is prepared into nano-composite fiber precursor in electrostatic spinning apparatus, electrospinning conditions are：
Voltage is 25kv, and distance of the syringe needle apart from substrate is 25cm, and solution feed rate is 1ml/h；
3) nano-composite fiber precursor made from step 2) is pre-oxidized 100~120 minutes at a temperature of 220~240 DEG C, so
After 950~1050 DEG C are warming up under inert atmosphere protection afterwards, it is passed through ammonia and carries out reaction 30~60 minutes, close after reaction
It closes ammonia and is passed through inert gas, furnace cooling obtains graphene nano pipe.
2. the preparation method of graphene nano pipe according to claim 1, which is characterized in that the graphene oxide is by micro-
Spar ink is prepared.
3. the preparation method of graphene nano pipe according to claim 1, which is characterized in that in step 1), when solvent is
During the arbitrary proportion mixture of n,N-Dimethylformamide or n,N-dimethylacetamide or the two, the solute is polypropylene
Nitrile.
4. the preparation method of graphene nano pipe according to claim 1, which is characterized in that in step 1), when solvent is
During water, the solute is any one of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl cellulose.
5. the preparation method of graphene nano pipe according to claim 1, which is characterized in that the inert gas is nitrogen
It is any in gas, argon gas, helium.
6. graphene nano pipe made from the preparation method described in any one of Claims 1 to 5 claim is preparing intelligence
Application in switching device.
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Cited By (1)
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|---|---|---|---|---|
| CN109205595A (en) * | 2018-09-27 | 2019-01-15 | 青岛大学 | Highly conductive Flexible graphene pipe and preparation method thereof |
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Cited By (2)
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| CN109205595A (en) * | 2018-09-27 | 2019-01-15 | 青岛大学 | Highly conductive Flexible graphene pipe and preparation method thereof |
| CN109205595B (en) * | 2018-09-27 | 2021-07-13 | 青岛大学 | High-conductivity flexible graphene tube and preparation method thereof |
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