CN107381557A - A kind of preparation method for mass producing graphene - Google Patents
A kind of preparation method for mass producing graphene Download PDFInfo
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- CN107381557A CN107381557A CN201710703677.5A CN201710703677A CN107381557A CN 107381557 A CN107381557 A CN 107381557A CN 201710703677 A CN201710703677 A CN 201710703677A CN 107381557 A CN107381557 A CN 107381557A
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Abstract
The invention belongs to technical field of graphene preparation, is related to a kind of preparation method of graphene, and in particular to a kind of to peel off graphite with liquid phase by high-temperature heating to mass produce the method for graphene.Graphene presoma is obtained from after by heating graphite and zinc powder, hot soarfing under protective atmosphere；Obtained graphene presoma is dissolved in the solution containing surfactant, ultrasound is peeled off and obtains graphene solution；Centrifuged successively again, be filtered, washed and dried processing, obtain graphene crude product；Then graphene crude product is subjected to microwave heating treatment, obtains graphene.The graphene purity and yield that the inventive method is prepared are higher, environmentally safe, simple to operate, have good application prospect.
Description
Technical field
The invention belongs to technical field of graphene preparation, is related to a kind of preparation method of graphene, and in particular to Yi Zhongtong
Cross high-temperature heating and peel off graphite with liquid phase to mass produce the method for graphene.
Background technology
2004, the physicist An Deliehaimu and Constantine's Nuo Woxiao loves of Univ Manchester UK,
By simple mechanical stripping method successfully isolated from graphite can individualism two-dimentional carbonizable substance-graphene, it is and right
Its property is measured and characterized, and shows its superior physical property, so as to start the prelude of graphene research.Two
Therefore scientist also obtains Nobel Prize in physics in 2010.Carbon as the newest form after fullerene, CNT is received
Rice material, graphene is since being reported, due to a series of novel physicochemical properties, such as ultrafast charge migration speed
Mechanical strength of degree, huge specific surface area and superelevation etc., is widely used in the electrochemical fields such as ultracapacitor, electro-catalysis.
But up to the present, the method for preparing graphene is not perfect.Specifically, current method can't
Prepare in yield and quality gratifying graphene simultaneously.Representative micromechanics stripping method and chemical vapor deposition
Method can prepare the pure graphene of high quality, but yield is too low, can not large-scale application；And the chemical oxidation generally used is also
Though former method energy prepare with scale graphene, gained graphene inevitably carry the defects of structure and composition, so as to
Reduce its superior electric property.
The content of the invention
The present invention is in order to avoid the existing deficiency prepared present in graphene technology, based on this, it is necessary to is provided a kind of
Cost is low, purity and yield are higher, environmentally safe, the preparation method of graphene simple to operate.
A kind of preparation method for mass producing graphene, comprises the following steps：
（1）Graphite is heated under protective atmosphere and zinc powder, hot soarfing obtain graphene presoma from after；
（2）The graphene presoma is dissolved in the solution containing surfactant, ultrasound is peeled off and obtains graphene solution；
（3）Obtained graphene solution is centrifuged successively, is filtered, washed and dried processing, obtains graphene crude product；
（4）Then graphene crude product is subjected to microwave heating treatment, obtains graphene.
Wherein the average grain diameter of graphite is 300~500 μm, and purity is 99~99.5%.
Wherein the average grain diameter of zinc powder is 3~15 μm, and purity is 99.7~99.9%.
Wherein the weight ratio of graphite and zinc powder is 1:15~20.
Step（1）Specially：By graphite and zinc powder in hybrid protection gas is passed through, 950 DEG C~1200 DEG C are heated to, place
The reason time is 10s~60s, reacts graphite and zinc powder, then carries out hot soarfing from obtaining graphene presoma；Or protecting
Under atmosphere, using 500~1500W microwave reactor by the graphite and zinc powder, 10s~5min is heated, makes graphite and zinc powder anti-
Should, hot soarfing is then carried out from obtaining graphene presoma.
Step（2）Middle surfactant is Tea Saponin；The concentration of surfactant solution is 5g/L~10g/L；Wherein stone
The solid-liquid ratio of black alkene presoma and both the aqueous solution containing surfactant is 0.05~0.1g/L.
Step（2）Ultrasonic strip step is that the solution dissolved with graphene presoma is ultrasonically treated into 20 minutes~40
12 hours~24 hours are stood after minute.
Step（3）Obtained graphene crude product, repeat step（2）To step（3）2 ~ 3 times.
Step（4）The power of middle microwave heating treatment is 500W~1500W, and the heat time is 60 seconds~120 seconds.
The advantages of above-mentioned preparation method, is：
1. using graphite as raw material, cheap cost is low, more easily peelable into graphene, and is greatly improved yield；
2. key to the invention is that it is that graphite and zinc powder react to obtain graphene presoma at high temperature heat.Illustrate：People
Common graphite be by from level to level with honeycomb-patterned ordered arrangement planar carbon atom stack and formed, the interlaminar action of graphite
Power is weaker, it is easy to peels off mutually, forms very thin graphite flake.After graphite flake is shelled into individual layer, a this only carbon
The individual layer of atomic thickness is exactly graphene.Graphite is Van der Waals force between layers, when graphite and zinc powder are in high-temperature heating, zinc
Powder (boiling point is at 902 DEG C or so), under the high temperature conditions, zinc powder is changed into gas phase, and the model moral of graphite layers is destroyed into graphite layers
Hua Li, graphite graphene presoma；
3. reagent is peeled off as intercalation using water and surfactant, it is safer, environmentally friendly and environmentally friendly；
4. the microwave heating treatment Jing Guo step 4, the hydrone in graphene and surfactant can be removed, obtained high-purity
The graphene of degree；
5. the equipment used is simple, easy to operate, production stage is few, is suitable for mass producing；
6. the parameters such as power, time by controlling microwave heating, can be easily adjusted the power to the processing of graphene crude product
Degree.In addition, microwave equipment start-stop is convenient, the advantages of having efficiently and save.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture for the sample that embodiment 1 is prepared.
Embodiment
For the further open rather than limitation present invention, below in conjunction with example, the present invention is described in further detail.
The preparation method of graphene comprises the following steps：
Step 1, there is provided graphite.The graphite is the graphite for meeting national standard GB/T 10698-1989, used in present embodiment
The average diameter of graphite is 300~500 μm, and purity is 99~99.5%, and the average grain diameter of zinc powder is 3~15 μm, and purity is
99.7~99.9%.The weight of graphite and zinc powder ratio is 1:15~20；
The graphite and zinc powder mixture are heated under protective atmosphere, hot soarfing obtains graphene presoma from after；In present embodiment,
Graphite and zinc powder are being passed through hybrid protection gas (2%~7%H of volume fraction2With 93%~98%Ar of volume fraction2)
Under the conditions of, 950 DEG C~1200 DEG C are heated to, processing time is 10s~60s, reacts graphite and zinc powder, then carries out hot soarfing
From obtaining graphene presoma；Or under protective atmosphere, using 500~1500W microwave reactor by the graphite and zinc
Powder, 10s~5min is heated, react graphite and zinc powder, then carry out hot soarfing from obtaining graphene presoma.
Step 2, obtained graphene presoma is dissolved into the solution containing surfactant, ultrasound is peeled off and obtains stone
Black alkene solution；In present embodiment, it is 5~10g/L containing surfactant that graphene presoma is added into concentration
In the aqueous solution, sonicated 20~40min, after standing 10~24h, it is molten to obtain the graphene that concentration is 0.05~0.1g/L
Liquid.
Surfactant has wetting or anti-stick, emulsification or demulsification, foaming or defoaming and solubilized, scattered, washing, anti-
The a series of physical chemical action such as rotten, antistatic.The main function of surfactant is so that graphene is good in the present invention
It scatter, the purpose of water is exactly that intercalation is peeled off so that graphene presoma is peeled off into graphene.Surfactant selects Tea Saponin.
Step 3, graphene solution centrifuged successively, be filtered, washed and dried processing, obtain graphene crude product.
In present embodiment, the graphene solution is centrifuged first, supernatant is collected, filtered, then uses deionized water
Cleaned repeatedly with ethanol, finally dried 2~5 hours with 80~100 DEG C of temperature in vacuum drying chamber, that is, obtain graphite
Alkene crude product.
Graphene crude product is carried out to the processing of the step 2 to 3 of 2 ~ 3 times again wherein, to improve graphene crude product
Yield and purity.
Step 4, the graphene crude product obtained to step 3 carries out microwave heating treatment, obtains graphene.This
In embodiment, microwave heating treatment is specially：The graphene crude product that step 3 obtains is put into microwave reactor,
Regulation microwave power is 500~1500W, heats 60~120s, high-purity so as to obtain to remove hydrone and surfactant
The graphene of degree.
Embodiment 1
(1) 300 μm of average diameter, the graphite of purity 99% are weighed；Average grain diameter be 5 μm, purity be 99.7% zinc powder, stone
The weight ratio of ink and zinc powder is 1:20；Graphite and zinc powder are being passed through hybrid protection gas (5%H2And 95%Ar2) condition
Under, 950 DEG C of processing 60s are heated to, hot soarfing is from rear, formation graphene presoma；
(2) the graphene presoma (25mg) in (1) is added to 250ml, concentration is 5mg/ml Tea Saponin solution
In, after ultrasonic 30min, 12h is stood, ultrasound is peeled off and forms graphene solution；
(3) graphene solution in (2) is subjected to centrifugation 30 minutes, supernatant is collected, filtered, use deionized water
Cleaned repeatedly with ethanol, finally obtain graphene crude product in vacuum drying chamber with 80 DEG C of dry 2h.
(4) the graphene crude product that (3) obtain is put into 1500W microwave reactor and heats 60s, remove moisture
Son and surfactant, obtain the graphene of high-purity.
Embodiment 2
(1) 400 μm of average diameter, the graphite of purity 99% are weighed；Average grain diameter is 5 μm, and purity is 99.7 % zinc powder.
The weight of graphite and zinc powder ratio is 1:18；Graphite and zinc powder are being passed through hybrid protection gas (5%H2And 95%Ar2) bar
Under part, 1050 DEG C of processing 60s are heated to, hot soarfing is from rear, formation graphene presoma；
(2) the graphene presoma (25mg) in (1) is added to 500ml, concentration is 50mg/ml Tea Saponin solution
In, after ultrasonic 30min, 24h is stood, ultrasound is peeled off and forms graphene solution；
(3) graphene solution in (2) is subjected to centrifugation 30min, supernatant is collected, filtered, use deionized water
Cleaned repeatedly with ethanol, finally obtain graphene crude product in vacuum drying chamber with 80 DEG C of dry 2h.
(4) sediment after centrifugation is repeated to the operation of (2)~(3), graphene crude product is obtained to improve
Yield.
(5) the graphene crude product in (4) is put into 500W microwave reactor and heated 120 seconds, remove moisture
Son and surfactant, obtain the graphene of high-purity.
Embodiment 3
(1) 400 μm of average diameter, the graphite of purity 99% are weighed；Average grain diameter is 8 μm, and purity is 99.9 % zinc powder,
The weight of graphite and zinc powder ratio is 1:17；Graphite and zinc powder are being passed through hybrid protection gas (5%H2And 95%Ar2) bar
Under part, 1100 DEG C of processing 60s are heated to, hot soarfing is from rear, formation graphene presoma；
(2) the graphene presoma (25mg) in (1) is added to 250ml, concentration is 5mg/ml Tea Saponin solution
In, after ultrasonic 30min, 12h is stood, ultrasound is peeled off and forms graphene solution；
(3) graphene solution in (2) is subjected to centrifugation 30 minutes, supernatant is collected, filtered, use deionization
Water and ethanol clean repeatedly, finally obtain graphene crude product in vacuum drying chamber with 80 DEG C of dry 2h.
(4) the graphene crude product in (3) is put into 600W microwave reactor and heats 60s, remove hydrone
And surfactant, obtain the graphene of high-purity.
Embodiment 4
(1) 400 μm of average diameter, the graphite of purity 99% are weighed；Average grain diameter is 8 μm, and purity is 99.9 % zinc powder,
The weight of graphite and zinc powder ratio is 1:16；Graphite and zinc powder are being passed through hybrid protection gas (5%H and 95%Ar2) bar
Under part, 1200 DEG C of processing 60s are heated to, hot soarfing is from rear, formation graphene presoma；
(2) the graphene presoma (25mg) in (1) is added to 250ml, concentration is 10mg/ml Tea Saponin solution
In, after ultrasonic 30min, 12h is stood, ultrasound is peeled off and forms graphene solution；
(3) graphene solution in (2) is subjected to centrifugation 30min, supernatant is collected, filtered, with deionized water and
Ethanol cleans repeatedly, finally obtains graphene crude product in vacuum drying chamber with 80 DEG C of dry 2h.
(4) sediment after centrifugation is repeated to the operation of (2)~(3), graphene crude product is obtained to improve
Yield.
(5) the graphene crude product in (4) is put into 600W microwave reactor and heated 60 seconds, remove hydrone
And surfactant, obtain the graphene of high-purity.
Fig. 1, it show transmission electron microscope (TEM) collection of illustrative plates of the graphene of the preparation of embodiment 1.As shown in Figure 1, this method
The higher graphite ene product of purity can be obtained, and the graphite ene product has good laminated structure.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (7)
- A kind of 1. preparation method for mass producing graphene, it is characterised in that：Comprise the following steps：（1）Graphite and zinc powder are mixed by hot soarfing from obtaining graphene presoma；（2）Obtained graphene presoma is dissolved in the solution containing surfactant, it is molten that ultrasound stripping obtains graphene Liquid；（3）Obtained graphene solution is centrifuged successively, is filtered, washed and dried processing, obtains graphene crude product；（4）By step（3）The graphene crude product of acquisition carries out microwave heating treatment, obtains graphene.
- A kind of 2. preparation method for mass producing graphene according to claim 1, it is characterised in that：Step（1）Specially：By graphite and zinc powder in the case where being passed through hybrid protection gas condition, 950 DEG C~1200 DEG C are heated to, place The reason time is 10s~60s, reacts graphite and zinc powder, then carries out hot soarfing from obtaining graphene presoma；Or it is：Under protective atmosphere, using 500~1500W microwave reactor by the graphite and zinc powder hot soarfing from heating 10s ~5min, obtain graphene presoma.
- A kind of 3. preparation method for mass producing graphene according to claim 1, it is characterised in that：Step（1）In The average grain diameter of graphite is 300~500 μm, and purity is 99~99.5%；The average grain diameter of zinc powder is 3~15 μm, and purity is 99.7~99.9%；Wherein the weight ratio of graphite and zinc powder is 1:15~20.
- A kind of 4. preparation method for mass producing graphene according to claim 1, it is characterised in that：Step（2）In Surfactant is Tea Saponin；The concentration of surfactant solution is 5g/L~10g/L；Wherein graphene presoma is with containing surface The solid-liquid ratio of both the aqueous solution of activating agent is 0.05~0.1g/L.
- A kind of 5. preparation method for mass producing graphene according to claim 1, it is characterised in that：Step（2）It is super It is specially to stand 12 hours~24 hours after being ultrasonically treated 20 minutes~40 minutes that sound, which is peeled off,.
- A kind of 6. preparation method for mass producing graphene according to claim 1, it is characterised in that：Step（3） The graphene crude product arrived, repeat step（2）To step（3）Step 2 ~ 3 time.
- A kind of 7. preparation method for mass producing graphene according to claim 1, it is characterised in that：Step（4）The power of middle microwave heating treatment is 500W~1500W, and the heat time is 60 s~120s.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030224168A1 (en) * | 2002-05-30 | 2003-12-04 | The Regents Of The University Of California | Chemical manufacture of nanostructured materials |
| US20110130494A1 (en) * | 2007-08-09 | 2011-06-02 | Centre National De La Recherche Scientifique - Cnrs | Graphene solutions |
| CN102815694A (en) * | 2012-03-13 | 2012-12-12 | 华东理工大学 | Graphene preparation method, and graphene prepared through using method |
| CN105244502A (en) * | 2015-08-28 | 2016-01-13 | 山东大学 | Method for preparing anode material of lithium ion battery by high-temperature reaction of expansible graphite and zinc powder |
| CN106395803A (en) * | 2016-09-09 | 2017-02-15 | 福州大学 | Biomass auxiliary preparation method and application of nitrogen doped graphene |
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2017
- 2017-08-16 CN CN201710703677.5A patent/CN107381557A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030224168A1 (en) * | 2002-05-30 | 2003-12-04 | The Regents Of The University Of California | Chemical manufacture of nanostructured materials |
| US20110130494A1 (en) * | 2007-08-09 | 2011-06-02 | Centre National De La Recherche Scientifique - Cnrs | Graphene solutions |
| CN102815694A (en) * | 2012-03-13 | 2012-12-12 | 华东理工大学 | Graphene preparation method, and graphene prepared through using method |
| CN105244502A (en) * | 2015-08-28 | 2016-01-13 | 山东大学 | Method for preparing anode material of lithium ion battery by high-temperature reaction of expansible graphite and zinc powder |
| CN106395803A (en) * | 2016-09-09 | 2017-02-15 | 福州大学 | Biomass auxiliary preparation method and application of nitrogen doped graphene |
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Application publication date: 20171124 |