CN107827104A - A kind of graphene oxide microballoon, the preparation method of graphene microballoon - Google Patents
A kind of graphene oxide microballoon, the preparation method of graphene microballoon Download PDFInfo
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- CN107827104A CN107827104A CN201711244099.XA CN201711244099A CN107827104A CN 107827104 A CN107827104 A CN 107827104A CN 201711244099 A CN201711244099 A CN 201711244099A CN 107827104 A CN107827104 A CN 107827104A
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Abstract
The invention discloses the preparation method of a kind of graphene oxide microballoon, graphene microballoon, comprise the following steps：The graphene oxide that modified Hummers ' methods will be used to prepare is scattered in deionized water, mass fraction is configured to as 0.2% 6% stable dispersion liquids, it is placed on again in spray gun hopper, balling-up is sprayed under 0.4 0.8Mpa pressure, and setting is freezed in liquid nitrogen, then by being freeze-dried to obtain graphene oxide microballoon no less than 4 hours, then by this graphene oxide microballoon through 400 1000 DEG C of high temperature cabonization process, heating rate is 25 DEG C/min, you can obtains graphene microballoon.By the change to nozzle diameter, 1 100 microns of microballoons not waited can be made, and the density of microballoon is no more than 50mg/cm3.The present invention is freezed through overspray and shaped, then prepare graphene oxide microballoon by freeze-drying by using water and only by the use of water as auxiliary agent, graphene microballoon is can obtain after carbonization, obtained Microsphere Density is ultralow, and preparation process is simple and environmentally-friendly, cost is relatively low, simple to operate, takes short.
Description
Technical field
The invention belongs to grapheme material field, and in particular to a kind of preparation of graphene oxide microballoon, graphene microballoon
Method.
Background technology
Graphene be one kind by carbon atom with sp2The hexangle type of hybridized orbit composition is in the flat film of honeycomb lattice, is
A kind of New Two Dimensional plane nano material with special monoatomic layer structure of discovered in recent years, the good, machine of conductive energy
The advantages that tool excellent performance, heat endurance are good, excellent in optical properties, big specific surface area.Graphene oxide on its surface due to containing
There are many polar groups, such as hydroxyl, carboxyl, epoxy radicals so that it is more easy to that good combination occurs between other materials, therefore
Many workers prepare graphene composite material using graphene oxide as intermediate.
These excellent properties of graphene oxide/graphene cause it to be led in absorption, conduction, heat conduction, electrochemistry, catalysis etc.
There is huge application prospect in domain.In order to make full use of the excellent properties of graphene oxide/graphene, prepare graphene oxide/
The three-dimensional material of graphene becomes the focus of researchers' research, and wherein micro-sphere structure is because its density is low, specific surface area is high
The advantages that and as most researchers optimal selection.
The existing method for preparing graphene oxide/graphene microballoon, exist using a variety of auxiliary agents, preparation process is complicated, into
This height, the deficiencies of time-consuming, preparation method could be improved.
The content of the invention
Present invention aims to overcome that the deficiencies in the prior art, there is provided a kind of simple, energy-conservation, the graphite oxide of high-efficiency environment friendly
The preparation method of alkene microballoon, graphene microballoon.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of graphene oxide microballoon, comprises the following steps：
（1）The graphene oxide prepared with modified Hummers ' methods is scattered in deionized water, being configured to mass fraction is
The graphene oxide dispersion of the stabilization of any one concentration between 0.2-6%；
（2）Graphene oxide dispersion is placed in the hopper of spray gun, balling-up is sprayed under 0.4-0.8Mpa pressure, and in liquid
It is freeze settled in nitrogen, obtain graphene oxide microballoon；
（3）Graphene oxide microballoon after will be freeze settled is freeze-dried, and sublimation drying is not less than 4 hours.
Further, step（1）Described in graphene oxide can be it is any can in water fine dispersion graphite oxide
The related substances of alkene.
Step（2）, by changing the nozzle diameter of spray gun, the particle diameter for controlling the graphene oxide microballoon being prepared is 1-
100 microns.
The nozzle diameter includes 0.2 millimeter, 0.3 millimeter and 0.5 millimeter, and the further expansion of nozzle diameter is available more
Large-sized microballoon.
Further, the density of the graphene oxide microballoon is no more than 50mg/cm3。
Present invention also offers a kind of preparation method of graphene microballoon, this method is the oxidation that the present invention is prepared
Graphene microballoon arrives graphene microballoon after high temperature cabonization.
Further, the carburizing temperature of carbonisation is 400-1000 DEG C.
The heating rate of carbonisation is 2-5 DEG C/min.
The preparation method of a kind of chitosan-graphene oxide microballoon, by mass fraction 0.2-6% graphene oxide solution
With mass fraction be 1-2% chitosan solution with 9:1 mass ratio mixing, obtains dispersion liquid, the sodium hydroxide for adding 0.1M is molten
Liquid ultrasonic disperse 10-20 minutes, is dialysed after 48h, dispersion liquid is placed in spray gun hopper, in 0.4- to dispersion liquid aobvious alkalescence
Balling-up is sprayed under 0.8Mpa pressure, and it is freeze settled in liquid nitrogen, chitosan-graphene oxide microballoon is obtained, freezing is fixed
Chitosan-graphene oxide microballoon after type is freeze-dried, and sublimation drying is not less than 4 hours.
A kind of preparation method of the graphene microballoon of N doping, chitosan-graphene oxide microballoon prepared by the present invention
It is placed in tube furnace, 400-1000 DEG C is warming up under 2-5 DEG C/min heating rate, is then incubated 2-2.5 hours, it is natural
After cooling, the graphene microballoon of N doping is obtained.
The present invention uses above technical scheme, by the use of water and only by the use of water as auxiliary agent, by spraying freeze forming, freeze-drying
Graphene oxide microballoon is prepared, graphene oxide microballoon can obtain graphene microballoon after high temperature cabonization, prepared by the inventive method
Process is simple and environmentally-friendly, and cost is relatively low, simple to operate, takes short.
The advantages of the present invention are：
1st, used auxiliary agent is only water, needs a variety of auxiliary agents different from other preparation methods, simple to operate, energy-conserving and environment-protective, into
This is cheap.
2nd, the concentration of raw material and dosage control range are wider, need precisely to use some reagents different from other preparation methods
Amount so that practical operation is more simple, and easily successfully obtains required product.
3rd, compared to other preparation methods, the inventive method, which has, is molded the characteristics of fast, and spray gun is i.e. plastic after spraying, no
Need to realize sizing by the complicated operation of multistep.
4th, invention can prepare graphene oxide/graphene microballoon without especial equipment requirements, typically conventional equipment.
5th, the present invention can obtain ultralight graphene oxide/graphene microballoon, and density is no more than 50mg/cm3。
6th, preparation process of the present invention is easy to operate, without too many technical operation, simple and fast, can be achieved to be prepared on a large scale.
7th, the present invention it is time-consuming it is short, technique is simple, energy-conserving and environment-protective, have a good application prospect.
8th, the present invention can prepare its corresponding microballoon by the material of fine dispersion suitable for most of water.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of graphene oxide microballoon prepared by embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of graphene microballoon prepared by embodiment 1；
Fig. 3 is chitosan-graphene oxide microballoon prepared by embodiment 5（A）With the graphene microballoon of N doping（B）Scanning electricity
Mirror figure.
Embodiment：
1st, a kind of preparation method of graphene oxide microballoon, comprises the following steps：
（1）The graphene oxide prepared with modified Hummers ' methods is scattered in deionized water, being configured to mass fraction is
The graphene oxide dispersion of the stabilization of any one concentration between 0.2-6%；
（2）Graphene oxide dispersion is placed in the hopper of spray gun, balling-up is sprayed under 0.4-0.8Mpa pressure, and in liquid
It is freeze settled in nitrogen, obtain graphene oxide microballoon；By changing the nozzle diameter of spray gun, the oxygen of 1-100 microns can be made
Graphite alkene microballoon, density are no more than 50mg/cm3；
（3）Graphene oxide microballoon after will be freeze settled is freeze-dried, and sublimation drying is not less than 4 hours.
2nd, a kind of preparation method of graphene microballoon, graphene oxide microballoon prepared by the present invention is placed in tube furnace,
400-1000 DEG C is warming up under 2-5 DEG C/min heating rate, and is incubated a period of time, after natural cooling, obtains graphene
Microballoon.
3rd, the preparation method of a kind of chitosan-graphene oxide microballoon, mass fraction 0.2-6% graphene oxide is molten
Liquid and mass fraction are 1-2% chitosan solution with 9:1 mass ratio mixing, obtains dispersion liquid, adds 0.1M sodium hydroxide
Solution ultrasonic disperse 10-20 minutes, is dialysed after 48h, dispersion liquid is placed in spray gun hopper, in 0.4- to dispersion liquid aobvious alkalescence
Balling-up is sprayed under 0.8Mpa pressure, and it is freeze settled in liquid nitrogen, chitosan-graphene oxide microballoon is obtained, freezing is fixed
Chitosan-graphene oxide microballoon after type is freeze-dried, and sublimation drying is not less than 4 hours.
4th, the preparation method of graphene microballoon chitosan-graphene oxide microballoon of a kind of N doping, prepared by the present invention
Chitosan-graphene oxide microballoon be placed in tube furnace, be warming up to 400-1000 under 2-5 DEG C/min heating rate
DEG C, 2-2.5 hours then are incubated, after natural cooling, obtain the graphene microballoon of N doping.
Embodiment 1
A kind of preparation method of graphene oxide/graphene microballoon
The graphene oxide aqueous dispersions that mass fraction is 1.6wt% are prepared, appropriate liquid nitrogen is loaded onto with rustless steel container, will aoxidize
Graphene dispersing solution is placed in spray gun hopper, nozzle diameter 0.2mm, and compressed air is connected in spray gun bottom, keeps pressure to exist
0.4-0.8Mpa or so, the graphene oxide in spray gun hopper is existed at nozzle distance liquefied ammonia height about 15-20cm height
Injection freeze forming into liquid nitrogen, then by the freeze-drying of 8 hours, obtains graphite oxide under the pressure that compressed air provides
Alkene microballoon.
Graphene oxide microballoon is placed in tube furnace 800 DEG C are warming up under 5 DEG C/min heating rate, and be incubated 2
Hour, after natural cooling, obtain graphene microballoon.
The scanning electron microscope (SEM) photograph of graphene oxide microballoon and graphene microballoon manufactured in the present embodiment is distinguished as illustrated in fig. 1 and 2,
As can be seen from the figure the graphene oxide microballoon and graphene microballoon of good pattern, and diameter is distributed in 1-30 μ ms.
Embodiment 2
A kind of preparation method of graphene oxide/graphene microballoon
25mg/ml graphene oxide aqueous dispersions are prepared, appropriate liquid nitrogen is loaded onto with rustless steel container, graphene oxide is disperseed
Liquid is placed in spray gun hopper, nozzle diameter 0.2mm, and compressed air is connected in spray gun bottom, keeps pressure in 0.4-0.8Mpa
Left and right, the graphene oxide in spray gun hopper is carried in compressed air at nozzle distance liquefied ammonia height about 15-20cm height
Injection freezes shaping into liquid nitrogen under the pressure of confession, afterwards by the freeze-drying of 6 hours, obtains graphene oxide microballoon, micro-
Bulb diameter is in 1-30 μ ms.
Graphene oxide microballoon is placed in tube furnace 1000 DEG C are warming up under 2 DEG C/min heating rate, and be incubated 2
Hour, after natural cooling, graphene microballoon is obtained, microsphere diameter is in 1-30 μ ms.
Embodiment 3
A kind of preparation method of graphene oxide/graphene microballoon
The graphene oxide aqueous dispersions that mass fraction is 0.4wt% are prepared, appropriate liquid nitrogen is loaded onto with rustless steel container, will aoxidize
Graphene dispersing solution is placed in spray gun hopper, nozzle diameter 0.3mm, and compressed air is connected in spray gun bottom, keeps pressure to exist
0.4-0.8Mpa or so, the graphene oxide in spray gun hopper is existed at nozzle distance liquefied ammonia height about 15-20cm height
Injection freezes shaping into liquid nitrogen under the pressure that compressed air provides, and afterwards by the freeze-drying of 5 hours, obtains graphite oxide
Alkene microballoon, microsphere diameter is in 5-50 μ ms.
Graphene oxide microballoon is placed in tube furnace 800 DEG C are warming up under 2 DEG C/min heating rate, and be incubated 2
Hour, after natural cooling, graphene microballoon is obtained, microsphere diameter is in 5-50 μ ms.
Embodiment 4
A kind of preparation method of graphene oxide/graphene microballoon
The graphene oxide aqueous dispersions that mass fraction is 0.4wt% are prepared, appropriate liquid nitrogen is loaded onto with rustless steel container, will aoxidize
Graphene dispersing solution is placed in spray gun hopper, nozzle diameter 0.5mm, and compressed air is connected in spray gun bottom, keeps pressure to exist
0.4-0.8Mpa or so, the graphene oxide in spray gun hopper is existed at nozzle distance liquefied ammonia height about 15-20cm height
Injection freezes shaping into liquid nitrogen under the pressure that compressed air provides, and afterwards by the freeze-drying of 5 hours, obtains graphite oxide
Alkene microballoon, microsphere diameter is in 10-100 μ ms.
Graphene oxide microballoon is placed in tube furnace 400 DEG C are warming up under 5 DEG C/min heating rate, and be incubated 2
Hour, after natural cooling, graphene microballoon is obtained, microsphere diameter is in 10-100 μ ms.
Embodiment 5
A kind of preparation method of graphene oxide/graphene microballoon
By mass fraction 1.6wt% graphene oxide and 2wt% chitosan solution（Solvent is 2wt% aqueous acetic acid）With
9:1 mass ratio is mixed to get dispersion liquid, and sodium hydroxide solution to the aobvious alkalescence of dispersion liquid, the ultrasonic disperse 10 for adding 0.1M divides
Clock, then after dialysis in 2 days, dispersion liquid is placed in spray gun hopper, nozzle diameter 0.2mm, it is empty that compression is connected in spray gun bottom
Gas, pressure is kept in 0.6 Mpa or so, by point in spray gun hopper at nozzle distance liquefied ammonia height about 15-20cm height
Dispersion liquid sprays into liquid nitrogen freezing shaping under the pressure that compressed air provides, and afterwards by the freeze-drying of 4 hours, obtains shell
Glycan-graphene oxide microballoon.
Chitosan-graphene oxide microballoon ball is placed in tube furnace and is warming up to 800 under 5 DEG C/min heating rate
DEG C, and 2 hours are incubated, after natural cooling, obtain the graphene microballoon of N doping.
The scanning electron microscope (SEM) photograph of the graphene microballoon of chitosan manufactured in the present embodiment-graphene oxide microballoon and N doping point
Not as shown in A, B in Fig. 3, the as can be seen from the figure graphite of the chitosan of good pattern-graphene oxide microballoon and N doping
Alkene microballoon, and diameter is distributed in 1-25 μ ms.
Claims (9)
- A kind of 1. preparation method of graphene oxide microballoon, it is characterised in that：It comprises the following steps：（1）The graphene oxide prepared with modified Hummers ' methods is scattered in deionized water, being configured to mass fraction is 0.2-6% graphene oxide dispersion；（2）Graphene oxide dispersion is placed in the hopper of spray gun, balling-up is sprayed under 0.4-0.8Mpa pressure, and in liquid It is freeze settled in nitrogen, obtain graphene oxide microballoon；（3）Graphene oxide microballoon after will be freeze settled is freeze-dried, and sublimation drying is not less than 4 hours.
- A kind of 2. preparation method of graphene oxide microballoon according to claim 1, it is characterised in that：Step（2）, change The nozzle diameter of spray gun, the particle diameter for controlling the graphene oxide microballoon being prepared are 1-100 microns.
- A kind of 3. preparation method of graphene oxide microballoon according to claim 2, it is characterised in that：The nozzle diameter Including 0.2 millimeter, 0.3 millimeter and 0.5 millimeter.
- A kind of 4. preparation method of graphene oxide microballoon according to claim 2, it is characterised in that：The graphite oxide The density of alkene microballoon is no more than 50mg/cm3。
- A kind of 5. preparation method of graphene microballoon, it is characterised in that：The oxidation that any preparation methods of claim 1-4 are obtained Graphene microballoon obtains graphene microballoon after high temperature cabonization.
- A kind of 6. preparation method of graphite alkene microballoon according to claim 5, it is characterised in that：The carbonization of carbonisation Temperature is 400-1000 DEG C.
- A kind of 7. preparation method of graphite alkene microballoon according to claim 6, it is characterised in that：The heating of carbonisation Speed is 2-5 DEG C/min.
- A kind of 8. preparation method of chitosan-graphene oxide microballoon, it is characterised in that：By mass fraction 0.2-6% oxidation stone Black alkene solution and mass fraction are 1-2% chitosan solution with 9:1 mass ratio mixing, obtains dispersion liquid, adds 0.1M hydrogen Sodium hydroxide solution is aobvious alkaline to dispersion liquid, ultrasonic disperse 10-20 minutes, dialyses after 48h, dispersion liquid is placed in spray gun hopper, Balling-up is sprayed under 0.4-0.8Mpa pressure, and it is freeze settled in liquid nitrogen, chitosan-graphene oxide microballoon is obtained, will Chitosan-graphene oxide microballoon after freeze settled is freeze-dried, and sublimation drying is not less than 4 hours.
- A kind of 9. preparation method of the graphene microballoon of N doping, it is characterised in that：The shell that claim 8 preparation method is obtained Glycan-graphene oxide microballoon is placed in tube furnace, 400-1000 DEG C is warming up under 2-5 DEG C/min heating rate, so 2-2.5 hours are incubated afterwards, after natural cooling, obtain the graphene microballoon of N doping.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109867270A (en) * | 2019-03-01 | 2019-06-11 | 北京化工大学 | A kind of preparation method and applications of carbon nano-material spherical shape assembly |
| CN110342516A (en) * | 2019-07-09 | 2019-10-18 | 哈尔滨工程大学 | A kind of MXene material of three-dimensional crosslinking structure and preparation method thereof |
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| CN105195067A (en) * | 2015-09-15 | 2015-12-30 | 四川大学 | Graphene aerogel microspheres and preparation method and application thereof |
| CN105859992A (en) * | 2016-04-01 | 2016-08-17 | 中南林业科技大学 | Urea-formaldehyde resin-based graphene oxide adsorption microsphere preparation method |
| CN107243326A (en) * | 2017-05-16 | 2017-10-13 | 北京化工大学 | A kind of preparation method of graphene oxide/chitosan composite aerogel microballoon |
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Patent Citations (4)
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| CN103121672A (en) * | 2013-03-20 | 2013-05-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene oxide microsphere and graphene microsphere and preparation methods thereof |
| CN105195067A (en) * | 2015-09-15 | 2015-12-30 | 四川大学 | Graphene aerogel microspheres and preparation method and application thereof |
| CN105859992A (en) * | 2016-04-01 | 2016-08-17 | 中南林业科技大学 | Urea-formaldehyde resin-based graphene oxide adsorption microsphere preparation method |
| CN107243326A (en) * | 2017-05-16 | 2017-10-13 | 北京化工大学 | A kind of preparation method of graphene oxide/chitosan composite aerogel microballoon |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109867270A (en) * | 2019-03-01 | 2019-06-11 | 北京化工大学 | A kind of preparation method and applications of carbon nano-material spherical shape assembly |
| CN109867270B (en) * | 2019-03-01 | 2021-06-08 | 北京化工大学 | Preparation method and application of nano carbon material spherical assembly |
| CN110342516A (en) * | 2019-07-09 | 2019-10-18 | 哈尔滨工程大学 | A kind of MXene material of three-dimensional crosslinking structure and preparation method thereof |
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