CN107673340B - The preparation method of graphene - Google Patents
The preparation method of graphene Download PDFInfo
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- CN107673340B CN107673340B CN201711170496.7A CN201711170496A CN107673340B CN 107673340 B CN107673340 B CN 107673340B CN 201711170496 A CN201711170496 A CN 201711170496A CN 107673340 B CN107673340 B CN 107673340B
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Abstract
The present invention relates to a kind of graphenes and preparation method thereof, and preparation method is successively comprising steps of first time crystalline flake graphite intercalation processing；First time Microwave Pretreatment；Mechanical refinement for the first time；Second of intercalation processing；Second of Microwave Pretreatment；Second of mechanical refinement；High-frequency ultrasonic oxidation；Microwave low-temperature reduction.The present invention is used as oxidant using the iron series oxidant of novel 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, at low cost, pollution-free, is suitable for industrializing large scale 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 preparation method of graphene.
Background technique
Graphene (Graphene) is the only one layer of atomic thickness for being stripped out from graphite material, being made of carbon atom
Two dimensional crystal.2004, Univ Manchester UK physicist An Deliegaimu and Constantine's Nuo Woxiao love,
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 breaking 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, the highest material of intensity.Graphene most potential application at present is to become silicon
Substitute, ultra micro transistor npn npn is manufactured, for producing following supercomputer.Replace silicon, computer disposal with graphene
The speed of service of device will be hundreds times fast.In addition, graphene is almost fully transparent, the light of absorption 2.3%.Another party
Face, it is very fine and close, even the smallest gas atom can not also penetrate.These features make it 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, the method for preparing graphene in the prior art, preparation process is relatively slow,
Layered effect is bad, therefore, it is also desirable to develop novel preparation method.
Summary of the invention
For the defects in the prior art, it is an object of that present invention to provide a kind of graphenes and preparation method thereof, to use
The iron series oxidant of novel 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, at low cost, pollution-free, is suitable for industrialization large scale preparation；The graphene reduction effect being prepared and dispersion
Effect is good.
To achieve the above object, technical solution provided by the invention are as follows:
The present invention provides a kind of preparation methods of graphene, successively comprising steps of first time crystalline flake graphite intercalation processing；
First time Microwave Pretreatment；Mechanical refinement for the first time；Second of intercalation processing；Second of Microwave Pretreatment；It is second mechanical thin
Change；High-frequency ultrasonic oxidation；Microwave low-temperature reduction.
First time crystalline flake graphite intercalation processing is that 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, carry out scale 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 reaction kettle, 30~35 DEG C of 70~80min of reaction；After completion of the reaction, product distilled water filtration washing reaction obtained, directly
To being in neutrality, then 45~55 DEG C of drying obtain being pre-mixed graphite for the first time.
First time Microwave Pretreatment specifically includes step: the product that first time crystalline flake graphite intercalation processing is obtained, and uses
Industrial microwave oven is in 260 DEG C of progress irradiation reactions.
Mechanical refinement specifically includes step for the first time: the product that first time Microwave Pretreatment is handled is ground,
Then 280 meshes are crossed, fine powder is collected；It is dry after fine powder is washed, obtain graphite powder.It should be noted that grinding preferably uses
High-speed grinder grinding.
Second of intercalation processing specifically includes step: being raw material by the product that mechanical refinement obtains for the first time, 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 mechanical refinement obtains for the first time
Object, potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid and potassium permanganate mass ratio be 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
Furnace is in 450~550 DEG C of progress irradiation reactions.
Second of mechanical 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 80 mesh screens, obtains nano-graphite dispersion liquid；By nanometer stone
The centrifugation of black dispersion liquid, collect it is dry after isolated solid, it is molten to remove then with 340~360 DEG C of microwave heating, 7~9min
Agent obtains nano oxidized graphite powder.
High-frequency ultrasonic oxidation is that the product for obtaining second of mechanical 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 mechanical refinement obtains
Object, potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid and potassium permanganate mass ratio be 1:6:0.8:35:35:0.08.
Preferably, high-frequency ultrasonic oxidation specifically includes step: the concentrated sulfuric acid being poured into dry reaction kettle, using ultrasound
Ice bath is cooled below 4 DEG C；Product, other intercalators and the oxidant that second of mechanical refinement is obtained are after mixing
It is added in reaction kettle, stands 65~75min；Ultrasound is closed, agitating device is opened and controls temperature of reaction system 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；It will reaction temperature
Degree is raised to 98 DEG C, continues constant temperature stirring, after filtering while hot, is washed with the dilute hydrochloric acid that mass fraction is 10%；After washing, take
Product is scattered in deionized water out, ultrasonic vibration 3 hours, obtains graphene oxide solution；By graphene oxide solution 78~
82 DEG C sufficiently dry, then grinds, and graphene oxide is made.
Microwave low-temperature reduction specifically includes step: product, the boron sodium oxide molybdena, hydrazine hydrate that high-frequency ultrasonic is aoxidized,
It is configured to solution with 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 disperses solution and is separated by solid-liquid separation, and collects solid, obtains graphene.
The present invention also protects the graphene being prepared according to the above method.
Technical solution provided by the invention, with following the utility model has the advantages that (1) is of the invention by using intercalation three times and oxygen
Change, and microwave and chemical method is combined to share reduction method, the graphene reduction effect and dispersion effect being prepared are good, and defect is few；
(2) present invention using novel non-toxic inexpensive iron series oxidant, instead of chlorine system, the manganese systems oxidant for continuing to use over half a century,
Make that graphene preparation process is fast, layered effect speed is fast, layering spacing is big, oxygen-containing functional group is sufficient, at low cost, pollution-free, fits
For industrialize large scale 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 generate oxygen, these gases can help its "top" layers apart layer stone
Ink makes to prepare speed quickening)；(3) include in the preparation method that uses of the present invention machinery refine, be ground up, sieved, more little particle into
Row layering oxidation etc., excellent.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Fig. 1 is the detection location drawing of the graphene sample 1# in the embodiment of the present invention in test condition 1；
Fig. 2 is Raman spectrogram of the graphene sample 1# in the embodiment of the present invention in test condition 1；
Fig. 3 is the detection location drawing of the graphene sample 1# in the embodiment of the present invention in test condition 2；
Fig. 4 is Raman spectrogram of the graphene sample 1# in the embodiment of the present invention in test condition 2；
Fig. 5 is shape appearance figure before test of the graphene sample 2# when detecting position 1 in the embodiment of the present invention；
Fig. 6 is shape appearance figure after test of the graphene sample 2# when detecting position 1 in the embodiment of the present invention；
Fig. 7 is Raman spectrogram of the graphene sample 2# when detecting position 1 in the embodiment of the present invention；
Fig. 8 is shape appearance figure before test of the graphene sample 2# when detecting position 2 in the embodiment of the present invention；
Fig. 9 is shape appearance figure after test of the graphene sample 2# when detecting position 2 in the embodiment of the present invention；
Figure 10 is Raman spectrogram of the graphene sample 2# when detecting 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.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description.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 is unless otherwise specified conventional side
Method.Test material as used in the following examples is unless otherwise specified to be commercially available from regular shops.Implement below
Quantitative test in example, is respectively provided with three repeated experiments, and data are the average value or mean+SD of three repeated experiments.
The present invention provides a kind of preparation method of graphene, successively comprising steps of first time crystalline flake graphite intercalation processing；The
Microwave Pretreatment；Mechanical refinement for the first time；Second of intercalation processing；Second of Microwave Pretreatment；Second of mechanical refinement；
High-frequency ultrasonic oxidation；Microwave low-temperature reduction, specific step is as follows.
1, first time crystalline flake graphite intercalation processing
Using phosphorus content for 99% crystalline flake graphite is raw material, 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 reaction kettle, 30~35 DEG C of 70~80min of reaction, after completion of the reaction,
The a large amount of distilled water filtration washing of product that reaction is obtained, until being in neutrality, then 45~55 DEG C of drying are obtained for the first time
It is pre-mixed graphite.
2, first time Microwave Pretreatment
It will be once pre-mixed graphite, using industrial microwave oven in 260 DEG C of progress irradiation reactions, generate expanded graphite.
3, mechanical refinement for the first time
Expanded graphite is ground with high-speed grinder, then crosses 280 meshes, collects fine powder；It is done after fine powder is washed
It is dry, obtain graphite powder.
4, 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, concentrated nitric acid and potassium permanganate mass ratio be 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 obtain second of premixing oxygen
Graphite.
5, second of Microwave Pretreatment
Graphite oxide will be pre-mixed second, using industrial microwave oven, in 450~550 DEG C of progress irradiation reactions.
6, second of mechanical 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 mesh screens, obtains nano-graphite dispersion liquid；Nano-graphite dispersion liquid is centrifuged, isolated consolidate is collected
It is dry after body, then with 340~360 DEG C of 7~9min of heating of microwave, obtain nano oxidized graphite powder.
7, high-frequency ultrasonic aoxidizes
High-frequency ultrasonic oxidation be by nano oxidized graphite powder be raw material, 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 reaction kettle, is cooled below 4 DEG C using ultrasonic ice bath；
Product, other intercalators and oxidant that second of mechanical refinement obtains are added in reaction kettle after mixing,
Stand 65~75min；
Cold stage: closing ultrasound, opens agitating device and controls temperature of reaction system no more than 20 DEG C, continues 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: being raised to 98 DEG C for reaction temperature, continues constant temperature stirring, is 10% with mass fraction after filtering while hot
Dilute hydrochloric acid washing；After washing, takes out product and be scattered in deionized water, ultrasonic vibration 3 hours, obtain graphene oxide
Solution；
It is sufficiently dry by 78~82 DEG C of graphene oxide solution, it then grinds, graphene oxide is made.
8, 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 obtains graphene suspension；
Graphene suspension is ultrasonically treated 25~35min in ultrasonic cleaner, obtains graphene dispersion solution；
Graphene dispersion solution is separated by solid-liquid separation, solid is collected, obtains graphene.
The preparation method of graphene provided by the invention is described further combined with specific embodiments below.
Embodiment
The present embodiment provides a kind of preparation methods of graphene, successively comprising steps of first time crystalline flake graphite intercalation processing；
First time Microwave Pretreatment；Mechanical refinement for the first time；Second of intercalation processing；Second of Microwave Pretreatment；It is second mechanical thin
Change；High-frequency ultrasonic oxidation；Microwave low-temperature reduction, specific step is as follows.
1, first time crystalline flake graphite intercalation processing
Using phosphorus content for 99% crystalline flake graphite is raw material, 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 reaction kettle, 32 DEG C of reaction 76min will react after completion of the reaction
The a large amount of distilled water filtration washing of the product arrived, until being in neutrality, then 50 DEG C of drying obtain being pre-mixed graphite for the first time.
2, first time Microwave Pretreatment
It will be once pre-mixed graphite, using industrial microwave oven in 260 DEG C of progress irradiation reactions, generate expanded graphite.
3, mechanical refinement for the first time
Expanded graphite is ground with high-speed grinder, then crosses 280 meshes, collects fine powder；It is done after fine powder is washed
It is dry, obtain graphite powder.
4, 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, concentrated nitric acid and potassium permanganate mass ratio be 1:5:
0.6:30:30:0.09.After all substances are mixed, 55 DEG C of high-speed stirred 2h obtain second of premixing graphite oxide.
5, second of Microwave Pretreatment
Graphite oxide will be pre-mixed second, using industrial microwave oven, in 500 DEG C of progress irradiation reactions.
6, second of mechanical 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 mesh screens, obtains nano-graphite dispersion liquid；Nano-graphite dispersion liquid is centrifuged, isolated consolidate is collected
It is dry after body, then with 350 DEG C of heating 8min of microwave, obtain nano oxidized graphite powder.
7, high-frequency ultrasonic aoxidizes
High-frequency ultrasonic oxidation be by nano oxidized graphite powder be raw material, 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 reaction kettle, is cooled below 4 DEG C using ultrasonic ice bath；
Product, other intercalators and oxidant that second of mechanical refinement obtains are added in reaction kettle after mixing,
Stand 70min；
Cold stage: closing ultrasound, opens agitating device and controls temperature of reaction system no more than 20 DEG C, continues 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: being raised to 98 DEG C for reaction temperature, continues constant temperature stirring, is 10% with mass fraction after filtering while hot
Dilute hydrochloric acid washing；After washing, takes out product and be scattered in deionized water, ultrasonic vibration 3 hours, obtain graphene oxide
Solution；
It is sufficiently dry by 80 DEG C of graphene oxide solution, it then grinds, graphene oxide is made.
8, 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 obtains graphene suspension；
Graphene suspension is ultrasonically treated 30min in ultrasonic cleaner, obtains graphene dispersion solution；
Graphene dispersion solution is separated by solid-liquid separation, solid is collected, obtains graphene.
The graphene dispersion solution that the embodiment of the present invention one is prepared, by function assessment test come its effect of system evaluation
Fruit.
1, first time Raman spectrum detects
Test sample: graphene dispersion solution, sample are in kermesinus, liquid, in plastic test tube；Two are taken when detection
Duplicate Samples are denoted 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 result
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 detection position of test condition 1 is as shown in Figure 1；Raman spectrogram is as shown in Figure 2；
The detection position of test condition 2 is as shown in Figure 3；Raman spectrogram is as shown in Figure 4.
(2) sample 2# test result
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 test of the sample 2# when detecting position 1；Shape appearance figure such as Fig. 6 institute after test
Show；Raman spectrogram is as shown in Figure 7.
Shape appearance figure is as shown in Figure 8 before test of the sample 2# when detecting position 2；Shape appearance figure is as shown in Figure 9 after test；Raman
Spectrogram is as shown in Figure 10.
From the above it is found that the peak D and G peak intensity of sample 1# and sample 2# are almost the same, the slightly above sample of sample 2#
Product 1#'s, 2D peak intensity is lower, tentatively judges graphene number of plies at five layers or less.
2, second of Raman spectrum detection
Test 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 (peak G) in graphene: 1578cm-1；
SP2 hydbridized carbon atoms ring around inhales the peak position (peak D) of vibration mode: 1330cm in graphene-1；
The vibration mode (peak 2D) of graphene lattice: 2600~2700cm-1。
It can be determined that by the peak 2D, which 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 term 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, it otherwise illustrates in these embodiments
Component and opposite 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 illustratively, not as limitation, because
This, other examples of exemplary embodiment can have different values.In the description of the present invention, it is to be understood that, term
" first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance or implicitly indicate meaning
The quantity of the technical characteristic shown.Define " first " as a result, the feature of " second " can explicitly or implicitly include one or
More this feature of person.In the description of the present invention, the meaning of " plurality " is two or more, unless otherwise clearly specific limit
It is fixed.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme should all cover in protection scope of the present invention.
Claims (1)
1. a kind of preparation method of graphene, which is characterized in that successively comprising steps of
First time crystalline flake graphite intercalation processing: using phosphorus content for 99% crystalline flake graphite is raw material, with potassium ferrate, five oxidations
Two phosphorus, the concentrated sulfuric acid, concentrated nitric acid and potassium permanganate are oxidant and intercalator, carry out crystalline flake graphite using the homogeneous graft process of high speed and insert
Layer processing；Wherein, the mass ratio of the crystalline flake graphite, potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid and potassium permanganate
For 1:4.5:0.30:30:30:0.1；Raw material, intercalator and oxidant are thrown in reaction kettle, 30~35 DEG C of reactions 70~
80min, after completion of the reaction, the product distilled water filtration washing that reaction is obtained, until being in neutrality, then 45~55 DEG C of bakings
It is dry, it obtains being pre-mixed graphite for the first time；
First time Microwave Pretreatment: the product that the first time crystalline flake graphite intercalation processing is obtained is existed using industrial microwave oven
260 DEG C of progress irradiation reactions；
Mechanical refinement for the first time: the product that the first time Microwave Pretreatment is handled is ground, 280 mesh are then crossed
Sieve collects fine powder；Will be dry after fine powder washing, obtain graphite powder；
Second of intercalation processing: the product that the first time machinery is refined 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, 54~56 DEG C of high speeds after all substances are mixed
1.8~2.2h is stirred, second of premixing graphite oxide is obtained；Wherein, the first time machinery refines product, high-speed rail
Sour potassium, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid and potassium permanganate mass ratio be 1:5:0.6:30:30:0.09；
Second of Microwave Pretreatment: the product that second of intercalation processing is obtained, using industrial microwave oven 450~550
DEG C carry out irradiation reaction；
Second mechanical refinement: the product that second of Microwave Pretreatment is obtained is raw material, and deionized water is solvent, with receiving
Rice grinder grinding, crosses 80 mesh screens for obtained defibrination, obtains nano-graphite dispersion liquid；By the nano-graphite dispersion liquid from
The heart, collects dry after isolated solid, then with 340~360 DEG C of 7~9min of heating of microwave, obtains nano oxidized graphite powder；
High-frequency ultrasonic oxidation: the concentrated sulfuric acid is poured into dry reaction kettle, is cooled below 4 DEG C using ultrasonic ice bath；
Product, other intercalators and oxidant that described second mechanical refinement obtains are added in reaction kettle after mixing,
Stand 65~75min；
Ultrasound is closed, agitating device is opened and controls temperature of reaction system 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 dilute hydrochloric acid that mass fraction is 10%；
After washing, takes out product and be scattered in deionized water, ultrasonic vibration 3 hours, obtain graphene oxide solution；
It is sufficiently dry by 78~82 DEG C of the graphene oxide solution, it then grinds, graphene oxide is made；
Wherein, it is raw material that high-frequency ultrasonic oxidation, which is the product for obtaining described second mechanical refinement, with potassium ferrate,
Phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid are intercalator, using potassium permanganate as catalytic oxidant；Wherein, described second mechanical thin
The mass ratio for changing obtained product, potassium ferrate, phosphorus pentoxide, the concentrated sulfuric acid, concentrated nitric acid and potassium permanganate is 1:6:0.8:35:
35:0.08；
Microwave low-temperature reduction: product, the boron sodium oxide molybdena, hydrazine hydrate that the high-frequency ultrasonic is aoxidized, it is high-purity with deionization
Water is configured to solution, is subsequently placed in micro-wave oven and irradiates 7min, obtains graphene suspension；By the graphene suspension super
It is ultrasonically treated 25~35min in sound wave washer, obtains graphene dispersion solution；Wherein, the high-frequency ultrasonic aoxidizes to obtain
Product, boron sodium oxide molybdena, hydrazine hydrate and deionization high purity water mass ratio be 1:25:25:30；By the graphene dispersion solution
It is separated by solid-liquid separation, collects solid, obtain the graphene.
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