CN107673340A - Graphene and preparation method thereof - Google Patents
Graphene and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of graphene and preparation method thereof, preparation method includes step successively：First time crystalline flake graphite intercalation processing；First time Microwave Pretreatment；Machinery refinement for the first time；Second of intercalation processing；Second of Microwave Pretreatment；Second of machinery refinement；High-frequency ultrasonic aoxidizes；Microwave low-temperature reduction.The present invention is used as oxidant using the iron system oxidant of new non-toxic inexpensive, makes that graphene preparation process is fast, layered effect speed is fast, layering spacing is big, oxygen-containing functional group is sufficient, cost is low, pollution-free, suitable for industrializing extensive preparation；The graphene reduction effect and dispersion effect being prepared are good.
Description
Technical field
The present invention relates to technical field of graphene preparation, and in particular to a kind of graphene and preparation method thereof.
Background technology
Graphene (Graphene) is the only one layer of atomic thickness for being stripped out from graphite material, being made up of carbon atom
Two dimensional crystal.2004, Univ Manchester UK physicist An Deliegaimu and Constantine's Nuo Woxiao loves,
Graphene is isolated in success from graphite, it was demonstrated that it can be with individualism.Graphene is both most thin material, and most tough
Material, 200 times more taller than best steel of fracture strength.It has good elasticity again simultaneously, and stretch range can reach itself
The 20% of size.It is that current nature is most thin, intensity highest material.Graphene most potential application at present is to turn into silicon
Substitute, manufacture ultra micro transistor npn npn, for produce future supercomputer.Substitute silicon, computer disposal with graphene
The speed of service of device will be fast hundreds times.In addition, graphene is almost fully transparent, 2.3% light is only absorbed.The opposing party
Face, it is very fine and close, even minimum gas atom can not also penetrate.These features cause it to be highly suitable as transparent electricity
The raw material of sub- product, such as transparent touch display screen, luminescent screen and solar panel.The synthetic method of graphene mainly has two
Kind：Mechanical means and chemical method.Mechanical means includes micromechanics partition method, epitaxy method and the method for heating SiC；Chemistry
Method is chemical reduction method and chemical dissociation method.However, preparing the method for graphene in the prior art, preparation process is relatively slow,
Layered effect is bad, therefore, it is also desirable to develop new preparation method.
The content of the invention
For in the prior art the defects of, present invention aims at a kind of graphene and preparation method thereof is provided, to use
The iron system oxidant of new non-toxic inexpensive, makes that graphene preparation process is fast, layered effect speed is fast, layering spacing is big, oxygen-containing official
Energy group is sufficient, cost is low, pollution-free, suitable for industrializing extensive preparation；The graphene reduction effect that is prepared and scattered
Effect is good.
To achieve the above object, technical scheme provided by the invention is：
The invention provides a kind of preparation method of graphene, successively including step：First time crystalline flake graphite intercalation processing；
First time Microwave Pretreatment；Machinery refinement for the first time；Second of intercalation processing；Second of Microwave Pretreatment；Second of machinery is thin
Change；High-frequency ultrasonic aoxidizes；Microwave low-temperature reduction.
First time crystalline flake graphite intercalation processing, be that to use phosphorus content for 99% crystalline flake graphite be raw material, with potassium ferrate,
Phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid and potassium permanganate are oxidant and intercalator, and scale is carried out using the homogeneous graft process of high speed
Graphite intercalation processing；Wherein, the quality of crystalline flake graphite, potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid and potassium permanganate
Than for 1:4.5:0.30:30:30:0.1.
Preferably, first time crystalline flake graphite intercalation processing specifically includes step：Raw material, intercalator and oxidant are thrown to
In reactor, 30~35 DEG C of 70~80min of reaction；After completion of the reaction, obtained product distilled water filtration washing will be reacted, directly
To in neutrality, then 45~55 DEG C of drying, premixing graphite for the first time is obtained.
First time Microwave Pretreatment specifically includes step：The product that first time crystalline flake graphite intercalation processing is obtained, use
Industrial microwave oven carries out irradiation reaction at 260 DEG C.
Machinery refinement for the first time specifically includes step：The product that first time Microwave Pretreatment handles to obtain is ground,
Then 280 mesh sieves are crossed, collect fine powder；Dried after fine powder is washed, obtain graphite powder.It should be noted that grinding preferably uses
High-speed grinder is ground.
Second of intercalation processing specifically includes step：The product that machinery refinement for the first time is obtained is raw material, with ferric acid
Potassium, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid are intercalator, using potassium permanganate as catalytic oxidant, 54 after all substances are mixed
~56 DEG C of 1.8~2.2h of high-speed stirred, obtain second of premixing graphite oxide；Wherein, the production that machinery refinement for the first time obtains
Thing, potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, the mass ratio of concentrated nitric acid and potassium permanganate are 1:5:0.6:30:30:0.09.
Second of Microwave Pretreatment specifically includes step：The product that second of intercalation processing is obtained, using industrial microwave
Stove carries out irradiation reaction at 450~550 DEG C.
Second of machinery refinement specifically includes step：The product that second of Microwave Pretreatment is obtained is raw material, deionization
Water is solvent, is ground with nano-level grinder, and obtained defibrination is crossed into 80 eye mesh screens, obtains nano-graphite dispersion liquid；By nanometer stone
The centrifugation of black dispersion liquid, dried after collecting isolated solid, then with 340~360 DEG C of microwave heating, 7~9min, it is molten to remove
Agent, obtain nano oxidized graphite powder.
High-frequency ultrasonic oxidation is that the product for obtaining second of machinery refinement is raw material, with potassium ferrate, five oxidations two
Phosphorus, the concentrated sulfuric acid, concentrated nitric acid are intercalator, using potassium permanganate as catalytic oxidant；Wherein, the production that second of machinery refinement obtains
Thing, potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, the mass ratio of concentrated nitric acid and potassium permanganate are 1:6:0.8:35:35:0.08.
Preferably, high-frequency ultrasonic oxidation specifically includes step：The concentrated sulfuric acid is poured into dry reactor, using ultrasound
Ice bath is cooled below 4 DEG C；After product, other intercalators and oxidant that second of machinery refinement obtains are well mixed
Add in reactor, stand 65~75min；Ultrasound is closed, agitating device is opened and controls temperature of reaction system to be no more than 20 DEG C,
Continue to stir 1.5h；Reaction temperature is rapidly brought up to 35 DEG C, after isothermal reaction 30min, is slowly added to deionized water；Will reaction temperature
Degree is raised to 98 DEG C, continues constant temperature stirring, after filtering while hot, is washed with the watery hydrochloric acid that mass fraction is 10%；After washing, take
Go out product to be scattered in deionized water, ultrasonic vibration 3 hours, obtain graphene oxide solution；By graphene oxide solution 78~
82 DEG C are fully dried, and are then ground, and graphene oxide is made.
Microwave low-temperature reduction specifically includes step：The product, boron sodium oxide molybdena, hydrazine hydrate that high-frequency ultrasonic is aoxidized to obtain,
Solution is configured to deionization high purity water, is subsequently placed in micro-wave oven, high-power lower irradiation 7min, obtains graphene suspension；
Graphene suspension is ultrasonically treated 25~35min in ultrasonic cleaner, obtains graphene dispersion solution；Wherein, high frequency
The mass ratio of product, boron sodium oxide molybdena, hydrazine hydrate and deionization high purity water that ultrasound oxidation technology obtains is 1:25:25:30；By graphite
Alkene dispersion soln separation of solid and liquid, solid is collected, obtains graphene.
The present invention also protects the graphene being prepared according to the above method.
Technical scheme provided by the invention, there is following beneficial effect：(1) present invention is by using intercalation three times and oxygen
Change, and combine microwave and the shared reducing process of chemical method, the graphene reduction effect and dispersion effect being prepared are good, and defect is few；
(2) present invention uses the iron system oxidant of new non-toxic inexpensive, instead of the chlorine system for continuing to use over half a century, manganese systems oxidant,
Make that graphene preparation process is fast, layered effect speed is fast, layering spacing is big, oxygen-containing functional group is sufficient, cost is low, pollution-free, fit
For industrialize extensive preparation (" running " speed of ferroxidant molecule is very fast, can as chock, quickly intert into
Enter inside graphite, make its fast hierarchical, in the process, can also produce oxygen, these gases can help its " top " layers apart layer stone
Ink, accelerate preparation speed)；(3) preparation method that uses of the present invention include machinery refinement, grinding, sieve, more little particle is entered
Row layering oxidation etc., excellent.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
Fig. 1 is test position figures of the graphene sample 1# in the embodiment of the present invention in test condition 1；
Fig. 2 is Raman spectrograms of the graphene sample 1# in the embodiment of the present invention in test condition 1；
Fig. 3 is test position figures of the graphene sample 1# in the embodiment of the present invention in test condition 2；
Fig. 4 is Raman spectrograms of the graphene sample 1# in the embodiment of the present invention in test condition 2；
Fig. 5 is shape appearance figure before tests of the graphene sample 2# in test position 1 in the embodiment of the present invention；
Fig. 6 is shape appearance figure after tests of the graphene sample 2# in test position 1 in the embodiment of the present invention；
Fig. 7 is Raman spectrograms of the graphene sample 2# in test position 1 in the embodiment of the present invention；
Fig. 8 is shape appearance figure before tests of the graphene sample 2# in test position 2 in the embodiment of the present invention；
Fig. 9 is shape appearance figure after tests of the graphene sample 2# in test position 2 in the embodiment of the present invention；
Figure 10 is Raman spectrograms of the graphene sample 2# in test position 2 in the embodiment of the present invention；
Figure 11 is the Raman spectrogram in second of Raman spectrum detection of graphene in the embodiment of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes.The following examples are only intended to illustrate the technical solution of the present invention more clearly, therefore is intended only as example, without
It can be limited the scope of the invention with this.Experimental method in following embodiments, it is conventional side unless otherwise specified
Method.Test material used, is to be commercially available from regular shops unless otherwise specified in following embodiments.Implement below
Quantitative test in example, it is respectively provided with and repeats to test three times, data is to repeat the average value or mean+SD of experiment three times.
The present invention provides a kind of preparation method of graphene, successively including step：First time crystalline flake graphite intercalation processing；The
Microwave Pretreatment；Machinery refinement for the first time；Second of intercalation processing；Second of Microwave Pretreatment；Second of machinery refinement；
High-frequency ultrasonic aoxidizes；Microwave low-temperature reduction, is comprised the following steps that.
1st, first time crystalline flake graphite intercalation processing
It for 99% crystalline flake graphite is raw material to use phosphorus content, with potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid
It is oxidant and intercalator with potassium permanganate；Crystalline flake graphite, potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid and permanganic acid
The mass ratio of potassium is 1:4.5:0.30:30:30:0.1；
Raw material, intercalator and oxidant are thrown in reactor, 30~35 DEG C of 70~80min of reaction, after completion of the reaction,
The substantial amounts of distilled water filtration washing of obtained product will be reacted, until in neutrality, then 45~55 DEG C of drying, obtains first time
It is pre-mixed graphite.
2nd, first time Microwave Pretreatment
Graphite will be once pre-mixed, irradiation reaction is carried out at 260 DEG C using industrial microwave oven, generates expanded graphite.
3rd, machinery refinement for the first time
Expanded graphite is ground with high-speed grinder, then crosses 280 mesh sieves, collects fine powder；Done after fine powder is washed
It is dry, obtain graphite powder.
4th, second of intercalation processing
It is raw material by graphite powder, using potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid as intercalator, with potassium permanganate
For catalytic oxidant, graphite powder, potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, the mass ratio of concentrated nitric acid and potassium permanganate are 1:5:
0.6:30:30:0.09.After all substances are mixed, 54~56 DEG C of 1.8~2.2h of high-speed stirred, second of premixing oxygen is obtained
Graphite.
5th, second of Microwave Pretreatment
Graphite oxide will be pre-mixed second, using industrial microwave oven, irradiation reactions are carried out at 450~550 DEG C.
6th, second of machinery refinement
The product that second of Microwave Pretreatment is obtained is raw material, and deionized water is solvent, is ground with nano-level grinder, will
Obtained defibrination crosses 80 eye mesh screens, obtains nano-graphite dispersion liquid；Nano-graphite dispersion liquid is centrifuged, collects isolated consolidate
Dried after body, then with 340~360 DEG C of microwave, 7~9min of heating, obtain nano oxidized graphite powder.
7th, high-frequency ultrasonic aoxidizes
It by nano oxidized graphite powder is raw material that high-frequency ultrasonic oxidation, which is, with potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid,
Concentrated nitric acid is intercalator, using potassium permanganate as catalytic oxidant；Nano oxidized graphite powder, potassium ferrate, phosphorus pentoxide, dense sulphur
The mass ratio of acid, concentrated nitric acid and potassium permanganate is 1:6:0.8:35:35:0.08；
High-frequency ultrasonic oxidation specifically includes step：
The concentrated sulfuric acid is poured into dry reactor, 4 DEG C are cooled below using ultrasonic ice bath；
Added after product, other intercalators and oxidant that second of machinery refinement obtains are well mixed in reactor,
Stand 65~75min；
Cold stage：Ultrasound is closed, agitating device is opened and controls temperature of reaction system to be no more than 20 DEG C, continue to stir
1.5h；
Middle thermophase：Reaction temperature is rapidly brought up to 35 DEG C, after isothermal reaction 30min, is slowly added to deionized water；
Hot stage：Reaction temperature is raised to 98 DEG C, continues constant temperature stirring, is 10% with mass fraction after filtering while hot
Watery hydrochloric acid washing；After washing, take out product and be scattered in deionized water, ultrasonic vibration 3 hours, obtain graphene oxide
Solution；
Graphene oxide solution is fully dried for 78~82 DEG C, then grinds, graphene oxide is made.
8th, microwave low-temperature reduction
By graphene oxide, boron sodium oxide molybdena, hydrazine hydrate, solution, graphene oxide, boron oxygen are configured to deionization high purity water
The mass ratio for changing sodium, hydrazine hydrate and deionization high purity water is 1:25:25:30；It is subsequently placed in micro-wave oven, high-power lower irradiation
7min, obtain graphene suspension；
Graphene suspension is ultrasonically treated 25~35min in ultrasonic cleaner, obtains graphene dispersion solution；
By graphene dispersion solution separation of solid and liquid, solid is collected, obtains graphene.
The preparation method of graphene provided by the invention is described further with reference to specific embodiment.
Embodiment
The present embodiment provides a kind of preparation method of graphene, successively including step：First time crystalline flake graphite intercalation processing；
First time Microwave Pretreatment；Machinery refinement for the first time；Second of intercalation processing；Second of Microwave Pretreatment；Second of machinery is thin
Change；High-frequency ultrasonic aoxidizes；Microwave low-temperature reduction, is comprised the following steps that.
1st, first time crystalline flake graphite intercalation processing
It for 99% crystalline flake graphite is raw material to use phosphorus content, with potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid
It is oxidant and intercalator with potassium permanganate；Crystalline flake graphite, potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid and permanganic acid
The mass ratio of potassium is 1:4.5:0.30:30:30:0.1；
Raw material, intercalator and oxidant are thrown in reactor, 32 DEG C of reaction 76min, after completion of the reaction, will be reacted
The substantial amounts of distilled water filtration washing of the product arrived, until in neutrality, then 50 DEG C of drying, obtain premixing graphite for the first time.
2nd, first time Microwave Pretreatment
Graphite will be once pre-mixed, irradiation reaction is carried out at 260 DEG C using industrial microwave oven, generates expanded graphite.
3rd, machinery refinement for the first time
Expanded graphite is ground with high-speed grinder, then crosses 280 mesh sieves, collects fine powder；Done after fine powder is washed
It is dry, obtain graphite powder.
4th, second of intercalation processing
It is raw material by graphite powder, using potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid as intercalator, with potassium permanganate
For catalytic oxidant, graphite powder, potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, the mass ratio of concentrated nitric acid and potassium permanganate are 1:5:
0.6:30:30:0.09.After all substances are mixed, 55 DEG C of high-speed stirred 2h, second of premixing graphite oxide is obtained.
5th, second of Microwave Pretreatment
Graphite oxide will be pre-mixed second, using industrial microwave oven, irradiation reactions are carried out at 500 DEG C.
6th, second of machinery refinement
The product that second of Microwave Pretreatment is obtained is raw material, and deionized water is solvent, is ground with nano-level grinder, will
Obtained defibrination crosses 80 eye mesh screens, obtains nano-graphite dispersion liquid；Nano-graphite dispersion liquid is centrifuged, collects isolated consolidate
Dried after body, then with 350 DEG C of microwave heating 8min, obtain nano oxidized graphite powder.
7th, high-frequency ultrasonic aoxidizes
It by nano oxidized graphite powder is raw material that high-frequency ultrasonic oxidation, which is, with potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid,
Concentrated nitric acid is intercalator, using potassium permanganate as catalytic oxidant；Nano oxidized graphite powder, potassium ferrate, phosphorus pentoxide, dense sulphur
The mass ratio of acid, concentrated nitric acid and potassium permanganate is 1:6:0.8:35:35:0.08；
High-frequency ultrasonic oxidation specifically includes step：
The concentrated sulfuric acid is poured into dry reactor, 4 DEG C are cooled below using ultrasonic ice bath；
Added after product, other intercalators and oxidant that second of machinery refinement obtains are well mixed in reactor,
Stand 70min；
Cold stage：Ultrasound is closed, agitating device is opened and controls temperature of reaction system to be no more than 20 DEG C, continue to stir
1.5h；
Middle thermophase：Reaction temperature is rapidly brought up to 35 DEG C, after isothermal reaction 30min, is slowly added to deionized water；
Hot stage：Reaction temperature is raised to 98 DEG C, continues constant temperature stirring, is 10% with mass fraction after filtering while hot
Watery hydrochloric acid washing；After washing, take out product and be scattered in deionized water, ultrasonic vibration 3 hours, obtain graphene oxide
Solution；
Graphene oxide solution is fully dried for 80 DEG C, then grinds, graphene oxide is made.
8th, microwave low-temperature reduction
By graphene oxide, boron sodium oxide molybdena, hydrazine hydrate, solution, graphene oxide, boron oxygen are configured to deionization high purity water
The mass ratio for changing sodium, hydrazine hydrate and deionization high purity water is 1:25:25:30；It is subsequently placed in micro-wave oven, high-power lower irradiation
7min, obtain graphene suspension；
Graphene suspension is ultrasonically treated 30min in ultrasonic cleaner, obtains graphene dispersion solution；
By graphene dispersion solution separation of solid and liquid, solid is collected, obtains graphene.
The graphene dispersion solution that the embodiment of the present invention one is prepared, by function assessment experiment come its effect of system evaluation
Fruit.
1st, first time Raman spectrum detects
Detect sample：Graphene dispersion solution, sample are in kermesinus, liquid, in plastic test tube；Two are taken during detection
Duplicate Samples, it is designated as sample 1#；Sample 2#.
Detection site：South China Science ＆ Engineering University's luminescent material and device National Key Laboratory；
(temperature：25~30 DEG C；Humidity：45%RH~60%RH；Air pressure：100kPa~101kPa)；
Detection time：On October 16,13 days~2017 October in 2017；
Detection device and instrument：Laser capture microdissection Raman spectrometer, RENISHAW inVia Reflex.
(1) sample 1# test results
Test condition 1
Laser：532nm；Time for exposure：10s；Laser power：10%；Cumulative number：1 time.
Test condition 2
Laser：532nm；Time for exposure：10s；Laser power：5%；Cumulative number：1 time.
As a result：The test position of test condition 1 is as shown in Figure 1；Raman spectrogram is as shown in Figure 2；
The test position of test condition 2 is as shown in Figure 3；Raman spectrogram is as shown in Figure 4.
(2) sample 2# test results
Test condition
Laser：532nm；Time for exposure：10s；Laser power：5%；Cumulative number：1 time.
As a result：Shape appearance figure is as shown in Figure 5 before tests of the sample 2# in test position 1；Shape appearance figure such as Fig. 6 institutes after test
Show；Raman spectrogram is as shown in Figure 7.
Shape appearance figure is as shown in Figure 8 before tests of the sample 2# in test position 2；Shape appearance figure is as shown in Figure 9 after test；Raman
Spectrogram is as shown in Figure 10.
Understand from the above, sample 1# and sample 2# D peaks and G peak intensities are basically identical, sample 2# slightly above sample
Product 1#'s, 2D peak intensities are relatively low, tentatively judge the graphene number of plies below five layers.
2nd, second of Raman spectrum detection
Detect sample：Graphene dispersion solution；
Detect unit：Zhaoqing Zhong Te can scientific and technological Investment Co., Ltd；
Detection time：On October 24th, 2017；
Detection device and instrument：633 lasers.
Testing result：Graphite Raman spectrogram is as shown in figure 11.
SP2 hydbridized carbon atoms peak position (G peaks) in graphene：1578cm-1；
SP2 hydbridized carbon atoms ring around inhales the peak position (D peaks) of vibration mode in graphene：1330cm-1；
The vibration mode (2D peaks) of graphene lattice：2600~2700cm-1。
It can be determined that by 2D peaks, the graphene sample belongs to multi-layer graphene, is 1~4 according to peak shape judgement sample
The admixed graphite alkene of layer.
It should be noted that unless otherwise indicated, technical term or scientific terminology used in this application should be this hair
The ordinary meaning that bright one of ordinary skill in the art are understood.Unless specifically stated otherwise, otherwise illustrate in these embodiments
Part and relative step, numerical expression and the numerical value of step are not limit the scope of the invention.It is illustrated and described herein
In all examples, unless otherwise prescribed, any occurrence should be construed as merely exemplary, not as limitation, because
This, other examples of exemplary embodiment can have different values.In the description of the invention, it is to be understood that term
" first ", " second " are only used for describing purpose, and it is not intended that instruction or implying relative importance or implicit indicating meaning
The quantity of the technical characteristic shown.Thus, define " first ", the feature of " second " can express or implicitly include one or
More this feature of person.In the description of the invention, " multiple " are meant that two or more, unless otherwise clearly specific limit
It is fixed.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, either which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme, it all should cover among protection scope of the present invention.
Claims (10)
1. a kind of preparation method of graphene, it is characterised in that successively including step：
First time crystalline flake graphite intercalation processing；First time Microwave Pretreatment；Machinery refinement for the first time；Second of intercalation processing；The
Secondary microwave pre-processes；Second of machinery refinement；High-frequency ultrasonic aoxidizes；Microwave low-temperature reduction.
2. the preparation method of graphene according to claim 1, it is characterised in that：
The first time crystalline flake graphite intercalation processing, be that to use phosphorus content for 99% crystalline flake graphite be raw material, with potassium ferrate,
Phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid and potassium permanganate are oxidant and intercalator, and scale is carried out using the homogeneous graft process of high speed
Graphite intercalation processing；Wherein, the crystalline flake graphite, potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid and potassium permanganate
Mass ratio is 1:4.5:0.30:30:30:0.1；
The first time crystalline flake graphite intercalation processing specifically includes step：Raw material, intercalator and oxidant are thrown to reactor
In, 30~35 DEG C of 70~80min of reaction, after completion of the reaction, the product distilled water filtration washing that reaction is obtained, until in being in
Property, then 45~55 DEG C of drying, obtain premixing graphite for the first time.
3. the preparation method of graphene according to claim 1, it is characterised in that the first time Microwave Pretreatment is specific
Including step：
The product that the first time crystalline flake graphite intercalation processing is obtained, irradiation reaction is carried out at 260 DEG C using industrial microwave oven.
4. the preparation method of graphene according to claim 1, it is characterised in that the specific bag of first time machinery refinement
Include step：
The product that the first time Microwave Pretreatment handles to obtain is ground, then crosses 280 mesh sieves, collects fine powder；By institute
Dried after stating fine powder washing, obtain graphite powder.
5. the preparation method of graphene according to claim 1, it is characterised in that second of intercalation processing is specifically wrapped
Include step：
The product that first time machinery refinement is obtained is raw material, with potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid
For intercalator, using potassium permanganate as catalytic oxidant, 54~56 DEG C of 1.8~2.2h of high-speed stirred, are obtained after all substances are mixed
To second of premixing graphite oxide；
Wherein, product, potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid and the Gao Meng that the first time machinery refinement obtains
The mass ratio of sour potassium is 1:5:0.6:30:30:0.09.
6. the preparation method of graphene according to claim 1, it is characterised in that second of Microwave Pretreatment is specific
Including step：
The product that second of intercalation processing is obtained, irradiation reaction is carried out at 450~550 DEG C using industrial microwave oven.
7. the preparation method of graphene according to claim 1, it is characterised in that the specific bag of second of machinery refinement
Include step：
The product that second of Microwave Pretreatment is obtained is raw material, and deionized water is solvent, is ground with nano-level grinder, will
Obtained defibrination crosses 80 eye mesh screens, obtains nano-graphite dispersion liquid；The nano-graphite dispersion liquid is centrifuged, collected isolated
Solid after dry, then with 340~360 DEG C of microwave, 7~9min of heating, obtain nano oxidized graphite powder.
8. the preparation method of graphene according to claim 1, it is characterised in that：
The high-frequency ultrasonic oxidation is that the product for obtaining second of the machinery refinement is raw material, with potassium ferrate, five oxygen
It is intercalator to change two phosphorus, the concentrated sulfuric acid, concentrated nitric acid, using potassium permanganate as catalytic oxidant；Wherein, second of the machinery refines
The mass ratio of the product, potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid and the potassium permanganate that arrive is 1:6:0.8:35:35:
0.08；
The high-frequency ultrasonic oxidation specifically includes step：
The concentrated sulfuric acid is poured into dry reactor, 4 DEG C are cooled below using ultrasonic ice bath；
Added after product, other intercalators and oxidant that second of the machinery refinement obtains are well mixed in reactor,
Stand 65~75min；
Ultrasound is closed, agitating device is opened and controls temperature of reaction system to be no more than 20 DEG C, continues to stir 1.5h；
Reaction temperature is rapidly brought up to 35 DEG C, after isothermal reaction 30min, is slowly added to deionized water；
Reaction temperature is raised to 98 DEG C, continues constant temperature stirring, after filtering while hot, is washed with the watery hydrochloric acid that mass fraction is 10%；
After washing, take out product and be scattered in deionized water, ultrasonic vibration 3 hours, obtain graphene oxide solution；
78~82 DEG C of the graphene oxide solution is fully dried, then ground, graphene oxide is made.
9. the preparation method of graphene according to claim 1, it is characterised in that the microwave low-temperature reduction specifically includes
Step：
The product, boron sodium oxide molybdena, hydrazine hydrate that the high-frequency ultrasonic is aoxidized to obtain, solution is configured to deionization high purity water,
It is subsequently placed in micro-wave oven and irradiates 7min, obtains graphene suspension；By the graphene suspension in ultrasonic cleaner
25~35min is ultrasonically treated, obtains graphene dispersion solution；Wherein, the high-frequency ultrasonic aoxidizes obtained product, boron oxidation
The mass ratio of sodium, hydrazine hydrate and deionization high purity water is 1:25:25:30；
By the graphene dispersion solution separation of solid and liquid, solid is collected, obtains the graphene.
10. the graphene that the method described in claim any one of 1-9 is prepared.
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| CN108399959A (en) * | 2018-03-08 | 2018-08-14 | 南通大学 | A kind of X, gamma-rays safeguard function raw powder's production technology |
| CN108598433A (en) * | 2018-04-24 | 2018-09-28 | 盐城师范学院 | A kind of SnO2The preparation method of/graphene lithium ion battery negative material |
| CN109231190A (en) * | 2018-11-02 | 2019-01-18 | 重庆大学 | Prepare redox graphene method and its redox graphene obtained |
| CN109336097A (en) * | 2018-09-07 | 2019-02-15 | 北京若水金枫科技有限公司 | A kind of preparation method and mass production device of graphene |
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