CN108046249A - A kind of preparation method of graphene - Google Patents
A kind of preparation method of graphene Download PDFInfo
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- CN108046249A CN108046249A CN201711372871.6A CN201711372871A CN108046249A CN 108046249 A CN108046249 A CN 108046249A CN 201711372871 A CN201711372871 A CN 201711372871A CN 108046249 A CN108046249 A CN 108046249A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 85
- 239000010439 graphite Substances 0.000 claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000008367 deionised water Substances 0.000 claims abstract description 39
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000002604 ultrasonography Methods 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 92
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- 239000011259 mixed solution Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 4
- 229940005991 chloric acid Drugs 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 239000000523 sample Substances 0.000 abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- 229960002163 hydrogen peroxide Drugs 0.000 description 21
- 230000005540 biological transmission Effects 0.000 description 13
- 239000010410 layer Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 8
- 239000000138 intercalating agent Substances 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 241000446313 Lamella Species 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- -1 alkene forms compound Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000005355 Hall effect Effects 0.000 description 1
- 206010020843 Hyperthermia Diseases 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036031 hyperthermia Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 229960001841 potassium permanganate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Abstract
The present invention discloses a kind of preparation method of graphene, belongs to graphene and preparing technical field.The method of the invention is：Oxidant and graphite are successively added in strong acid, it is uniformly mixed in 0 ~ 15 DEG C of water-bath, then certain bath temperature is kept, 0.5 ~ 3h is persistently stirred to react, mixed liquor is added dropwise in deionized water and water temperature is kept to add hydrogen peroxide less than 10 DEG C, react 5 ~ 20min, then it is stored in refrigerator, under the conditions of less than 15 DEG C, preserves a period of time；Intercalated graphite solution deionized water is replaced cleaning solution respectively three times with dilute hydrochloric acid, then with deionized water rinse solution to neutrality, is added in certain density aqueous slkali, mixing, 0.5 ~ 3h of ultrasound obtains graphene in Probe Ultrasonic Searching instrument afterwards.Quality that the present invention prepares graphene is high, using equipment it is few, it is simple for process, safe and reliable, easy to operation, of low cost, can be mass graphene.
Description
Technical field
The present invention relates to a kind of preparation methods of graphene, belong to graphene and preparing technical field.
Background technology
Since graphene in 2004 is found, the extensive concern of scientific research circle is caused, because of its unique hexangle type bee
Nest lattice plane structure makes it have many excellent performances.For example,（1）Quantum hall effect is observed at normal temperatures；（2）
With two-dimentional dirac fermion；（3）Higher thermal conductivity（5000W·m-1·K-1）, very big yang type modulus (1.0TPa)；
（4）Up to 2600m2The theoretical specific surface area of/g；（5）At room temperature, electron mobility is up to 15000cm2/（V·s）Deng.Due to
Graphene has the performance of above-mentioned excellent physics, chemistry, electronics etc., makes it have extremely wide application.For example, stone
Black alkene forms compound with lithium ion battery anode material, can greatly improve the capacitive character of battery；Graphene is applied to super
The fields such as capacitor, biosensor, material for water treatment, solar cell, transparent electrode.
However it is to limit one of its widely applied principal element that low cost, which prepares high-quality graphene,.Nearest more than ten
Nian Jian, the preparation method of graphene continue to bring out, for example, mechanical stripping method can prepare the graphene of high-quality, but mass
Production is difficult；Carborundum（SiC）Epitaxial growth method large batch of can prepare graphene, but the quality of graphene prepared is low.It is existing
The method that stage most generally prepares graphene is chemical gas phase growth methods（CVD）With oxidation-reduction method, CVD processes it is more complicated and into
This is excessively high；The graphene defect level that oxidation-reduction method takes and prepares is high.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation method of graphene so that graphene preparation manipulation
Convenient, simple for process, safe and reliable, of low cost, the graphene defect of preparation is few, the number of plies is few；In order to realize foregoing invention mesh
, present invention employs following technical solutions：
A kind of preparation method of graphene, comprises the following steps：
（1）The preparation of intercalated graphite：By graphite：Oxidant：The proportioning of strong acid is 0.5 ~ 3g:0.5~3g:The ratio of 20 ~ 120ml,
Oxidant is charged first to mixing in strong acid, graphite is added and is uniformly mixed in 0 ~ 15 DEG C of water-bath, then in 0 ~ 15 DEG C of water-bath
In be stirred to react 0.5 ~ 3h and obtain mixed solution A；Mixed solution A is taken out to be added dropwise in deionized water and water temperature is kept to be less than 15
DEG C, then by mixed solution A and hydrogen peroxide volume ratio be 5:1 ratio adds in the hydrogen peroxide that mass percent concentration is 37%
Solution stirs 5 ~ 20min, water temperature less than keep 1 under conditions of 15 DEG C ~ for 24 hours, obtain intercalated graphite solution；
（2）The preparation of graphene：Step（1）In intercalated graphite solution deionized water with dilute hydrochloric acid to replace cleaning solution each
Three times, then through deionized water rinse solution to neutrality, solution is then added to mixing in aqueous slkali, is surpassed afterwards under Ultrasound Instrument
Sound disperses 0.5 ~ 3h and obtains graphene.
Step of the present invention（1）In oxidant for iron chloride, potassium permanganate, hydrogen peroxide, chloric acid, hypochlorous acid, perchloric acid, nitre
One kind in acid, potassium bichromate, sodium hypochlorite.
The present invention works as step（1）In oxidant be hydrogen peroxide when, graphite is first added to mixing in hydrogen peroxide, is added
Strong acid.
Step of the present invention（1）In strong acid be sulfuric acid, nitric acid or the mixture for both being.
Step of the present invention（1）The temperature of middle drying process is 50 ~ 100 DEG C.
Step of the present invention（2）In aqueous slkali be sodium hydroxide solution, one or both of potassium hydroxide solution it is mixed
Object is closed, concentration is 0.5 ~ 10mol/L；The concentration of dilute hydrochloric acid is 1mol/L.
Step of the present invention（2）The power of middle Ultrasound Instrument is 200 ~ 800W.
Step of the present invention（2）Obtained graphene can be directly deposited in aqueous slkali or be centrifuged, be freeze-dried or
Drying obtains graphene powder.
The present invention prepares graphene using graft process, by graphite dispersion in oxidant and intercalator, is made using weak oxide
With, it is reacted with graphite surface and edge active site, the deformation of graphite surface layer is caused to increase with edge interlamellar spacing, oxidant entrance
Interlayer is further reacted with the active site in graphite linings, further expands the interlamellar spacing of graphite, as oxidant enters graphite linings
Between, the intercalator for being attached to graphite surface is caused constantly to be inserted into graphite layers and forms graphite intercalation compound.In this course,
If oxidability is too strong, every layer of graphite is all aoxidized, and has completely penetrated through graphite thickness, and the diffusion for causing intercalator is anti-
It should can not be carried out with intercalation, cause peroxidating and form " kish ", so as to be unfavorable for the stripping of graphite linings.Then,
Solution is preserved under cryogenic, prevents the peroxidating of graphite and high temperature from the intercalator in intercalation compound being caused to decompose, this
Sample can reduce graphite layers away from the difficulty that increase graphite is removed.Intercalation compound is dispersed in further intercalation in aqueous slkali, from
And increase graphite layers away from and the graphene dispersing solution that is conducive to, prevent the lamination of graphene layer.Pass through the energy of ultrasonic wave
Amount directly removes single-layer or multi-layer graphene from graphite surface, meanwhile, the high pressure that ultrasound generates causes graphite with localized hyperthermia
The intercalator of alkene layer surface decomposes, and so as to obtain graphene dispersing solution, maintains the complete pattern of graphene.
The method that the present invention prepares poroid graphene includes following advantageous effect：
（1）The present invention removes to prepare graphene using weak oxide-intercalation-ultrasound so that step is more succinct, the graphite of preparation
Alkene lamella is big, and defect is few.
（2）The present invention uses cheap graphite as raw material, simple for process, operating aspect so that this method operation is relatively pacified
Entirely, it is of low cost, it is easy to accomplish prepare with scale graphene has important impetus to the popularization and application of graphene.
Description of the drawings
Before Fig. 1 is embodiment 1 not ultrasound, the scanning electron microscope (SEM) photograph of intermediate product（SEM）；
Before Fig. 2 is embodiment 1 not ultrasound, the X-ray diffractogram (XRD) of intermediate product；
Fig. 3 obtains the transmission electron microscope picture (TEM) of graphene for embodiment 1；
Fig. 4 obtains the electron diffraction diagram (ED) of graphene for embodiment 1；
Fig. 5 obtains the Raman spectrogram of graphene for embodiment 1；
Fig. 6 obtains the transmission electron microscope picture of graphene for embodiment 3；
Fig. 7 obtains the transmission electron microscope picture of graphene for embodiment 4；
Fig. 8 obtains the transmission electron microscope picture of graphene for embodiment 6；
Fig. 9 obtains the transmission electron microscope picture of graphene for embodiment 8；
Figure 10 obtains the transmission electron microscope picture of graphene for embodiment 9；
Figure 11 obtains the transmission electron microscope picture of graphene for embodiment 10.
Specific embodiment
The present invention is described in further detail in the following with reference to the drawings and specific embodiments, but protection scope of the present invention is simultaneously
It is not limited to the content.
Embodiment 1
（1）The preparation of intercalated graphite：By graphite：Potassium permanganate：Proportioning=1g of sulfuric acid:1g:30ml first adds in potassium permanganate
In sulfuric acid, mixing, add graphite, which is uniformly mixed in 15 DEG C of water-baths, then reacts 1h in 15 DEG C of stirred in water bath
Obtain mixed solution A；Mixed solution A is taken out to be added dropwise in deionized water and keep 10 DEG C of water temperature, then by mixed solution A
It is 5 with hydrogen peroxide volume ratio:1 ratio adds in the hydrogenperoxide steam generator that mass percent concentration is 37% and stirs 5min, will be molten
Liquid is stored in refrigerator, and 12h is preserved at 15 DEG C and obtains intercalated graphite solution.
（2）The preparation of graphene：Step（1）In intercalated graphite solution deionized water and dilute hydrochloric acid（1mol/L）It hands over
For cleaning solution respectively three times, then through deionized water rinse solution to neutrality, then sodium hydroxide that solution is added to 1ml/L is molten
In liquid, mixing, ultrasound 1h, obtained graphene are stored in sodium hydroxide solution under 200 W Probe Ultrasonic Searching instrument afterwards.
In the present embodiment ultrasound before intermediate product scanning electron microscope (SEM) photograph（SEM）, as shown in Figure 1, the X-ray of intermediate product
Diffraction pattern (XRD) as shown in Fig. 2, the transmission electron microscope picture (TEM) for the graphene that the present embodiment is prepared as shown in figure 3, electronics
Diffraction pattern (ED) as shown in figure 4, Raman spectrogram as shown in figure 5, as seen from Figure 1, the stratiform of intercalated graphite has separated
Trend, from Fig. 2 ~ 5 it can be seen that the graphene better crystallinity degree prepared, lamella is big, and the number of plies is few, and defect is few.
Embodiment 2
（1）The preparation of intercalated graphite：By graphite：Iron chloride：Proportioning=1g of sulfuric acid:1g:Iron chloride is first added in sulfuric acid by 30ml
In, mixing, add graphite, which is uniformly mixed in 15 DEG C of water-baths, is then obtained in 15 DEG C of stirred in water bath reaction 1h
Mixed solution A；Mixed solution A is taken out to be added dropwise in deionized water and keep 10 DEG C of water temperature, then by mixed solution A and mistake
Hydrogen oxide volume ratio is 5:1 ratio adds in the hydrogenperoxide steam generator that mass percent concentration is 37% and stirs 5min, and solution is deposited
It is placed in refrigerator, 12h is preserved at 15 DEG C and obtains intercalated graphite solution.
（2）The preparation of graphene：Step（1）In intercalated graphite solution deionized water and dilute hydrochloric acid（1mol/L）It hands over
For cleaning solution respectively three times, then through deionized water rinse solution to neutrality, then sodium hydroxide that solution is added to 1ml/L is molten
In liquid, mixing, ultrasound 1h, obtained graphene are stored in sodium hydroxide solution under 200 W Probe Ultrasonic Searching instrument afterwards.
Embodiment 3
（1）The preparation of intercalated graphite：By graphite：Chloric acid：Proportioning=1g of sulfuric acid:1g:Chloric acid is first added in sulfuric acid, is mixed by 30ml
It is even, graphite is added, which is uniformly mixed in 15 DEG C of water-baths, then obtains mixing in 15 DEG C of stirred in water bath reaction 1h molten
Liquid A；Mixed solution A is taken out to be added dropwise in deionized water and keep 10 DEG C of water temperature, then by mixed solution A and hydrogen peroxide
Volume ratio is 5:1 ratio adds in the hydrogenperoxide steam generator that mass percent concentration is 37% and stirs 5min, and solution is stored in ice
In case, preservation 12h obtains intercalated graphite solution at 15 DEG C.
（2）The preparation of graphene：Step（1）In intercalated graphite solution deionized water and dilute hydrochloric acid（1mol/L）It hands over
For cleaning solution respectively three times, then through deionized water rinse solution to neutrality, then sodium hydroxide that solution is added to 1ml/L is molten
In liquid, mixing, ultrasound 1h, obtained graphene are stored in sodium hydroxide solution under 200W Probe Ultrasonic Searching instrument afterwards, this reality
The transmission electron microscope picture (TEM) for the graphene that example is prepared is applied as shown in fig. 6, the graphene sheet layer prepared as seen from the figure
Greatly, the number of plies is few.
Embodiment 4
（1）The preparation of intercalated graphite：By graphite：Perchloric acid：Proportioning=1g of nitric acid:1g:Perchloric acid is first added in nitric acid by 30ml
In, mixing, add graphite, which is uniformly mixed in 15 DEG C of water-baths, is then obtained in 15 DEG C of stirred in water bath reaction 1h
Mixed solution A；Mixed solution A is taken out to be added dropwise in deionized water and keep 10 DEG C of water temperature, then by mixed solution A and mistake
Hydrogen oxide volume ratio is 5:1 ratio adds in the hydrogenperoxide steam generator that mass percent concentration is 37% and stirs 5min, and solution is deposited
It is placed in refrigerator, 12h is preserved at 15 DEG C and obtains intercalated graphite solution.
（2）The preparation of graphene：Step（1）In intercalated graphite solution, by deionized water and dilute hydrochloric acid（1 mol/
L）Alternately solution respectively three times, then through deionized water rinse solution to neutrality, is then added to the hydroxide of 1ml/L by cleaning solution
In potassium solution, mixing, ultrasound 1h, obtained graphene are stored in potassium hydroxide solution under 200 W Probe Ultrasonic Searching instrument afterwards,
For the transmission electron microscope picture (TEM) for the graphene that the present embodiment is prepared as shown in fig. 7, lamella is big as seen from the figure, the number of plies is few.
Embodiment 5
（1）The preparation of intercalated graphite：By graphite：Nitric acid：Proportioning=1g of sulfuric acid:1g:Nitric acid is first added in sulfuric acid, is mixed by 30ml
It is even, graphite is added, which is uniformly mixed in 15 DEG C of water-baths, then obtains mixing in 15 DEG C of stirred in water bath reaction 3h molten
Liquid A；Mixed solution A is taken out to be added dropwise in deionized water and keep 10 DEG C of water temperature, then by mixed solution A and hydrogen peroxide
Volume ratio is 5:1 ratio adds in the hydrogenperoxide steam generator that mass percent concentration is 37% and stirs 5min, and solution is stored in ice
In case, preservation 12h obtains intercalated graphite solution at 15 DEG C.
（2）The preparation of graphene：Step（1）In intercalated graphite solution, by deionized water and dilute hydrochloric acid（1 mol/
L）Alternately solution respectively three times, then through deionized water rinse solution to neutrality, is then added to the hydroxide of 1ml/L by cleaning solution
In potassium solution, mixing, ultrasound 1h, obtained graphene dispersing solution are centrifuged under 200W Probe Ultrasonic Searching instrument afterwards, and
It is dried at 60 DEG C, obtains graphene powder.
Embodiment 6
（1）The preparation of intercalated graphite：By graphite：Potassium bichromate：Proportioning=1g of sulfuric acid:1g:30ml first adds in potassium bichromate
In nitric acid, mixing, add graphite, which is uniformly mixed in 15 DEG C of water-baths, then reacts 1h in 15 DEG C of stirred in water bath
Obtain mixed solution A；Take out the water temperature that mixed solution A is added dropwise in deionized water and is kept for 10 DEG C, then by mixed solution A with
Hydrogen peroxide volume ratio is 5:1 ratio adds in the hydrogenperoxide steam generator that mass percent concentration is 37% and stirs 5 min, will be molten
Liquid is stored in refrigerator, and 12h is preserved at 15 DEG C and obtains intercalated graphite solution.
（2）The preparation of graphene：Step（1）In intercalated graphite solution deionized water and dilute hydrochloric acid（1mol/L）It hands over
For cleaning solution respectively three times, then through deionized water rinse solution to neutrality, then sodium hydroxide that solution is added to 1ml/L is molten
In liquid, mixing, ultrasound 1h, obtained graphene dispersing solution are centrifuged under 200W Probe Ultrasonic Searching instrument afterwards, and at 60 DEG C
Lower drying, obtains graphene powder.
Embodiment 7
（1）The preparation of intercalated graphite：By graphite：Sodium hypochlorite：Proportioning=3g of sulfuric acid:3g:60ml first adds in sodium hypochlorite
In sulfuric acid, mixing, add graphite, which is uniformly mixed in 15 DEG C of water-baths, then reacts 1h in 15 DEG C of stirred in water bath
Obtain mixed solution A；Mixed solution A is taken out to be added dropwise in deionized water and keep 10 DEG C of water temperature, then by mixed solution A
It is 5 with hydrogen peroxide volume ratio:1 ratio adds in the hydrogenperoxide steam generator that mass percent concentration is 37% and stirs 5 min, will
Solution is stored in refrigerator, and 12h is preserved at 15 DEG C and obtains intercalated graphite solution.
（2）The preparation of graphene：Step（1）In intercalated graphite solution deionized water and dilute hydrochloric acid（1mol/L）It hands over
For cleaning solution respectively three times, and addition is 100ml every time, then through deionized water rinse solution to neutrality, then solution is added
Enter into the sodium hydroxide solution of 10ml/L, mixing, afterwards the ultrasound 1h under 200W Probe Ultrasonic Searching instrument, obtained graphene storage
In sodium hydroxide solution.
Embodiment 8
（1）The preparation of intercalated graphite：By graphite：Potassium permanganate：Proportioning=0.5g of sulfuric acid:0.5g:30ml, potassium permanganate is first
It adds in sulfuric acid, mixing, adds graphite, which is uniformly mixed in 15 DEG C of water-baths, then anti-in 15 DEG C of stirred in water bath
1h is answered to obtain mixed solution A；Mixed solution A is taken out to be added dropwise in deionized water and keep 10 DEG C of water temperature, then by mixing
Solution A is 5 with hydrogen peroxide volume ratio:1 ratio adds in the hydrogenperoxide steam generator that mass percent concentration is 37% and stirs
Solution is stored in refrigerator by 5min, and 12h is preserved at 15 DEG C and obtains intercalated graphite solution.
（2）The preparation of graphene：Step（1）In intercalated graphite solution deionized water and dilute hydrochloric acid（1mol/L）It hands over
For cleaning solution respectively three times, and addition is 100ml every time, then through deionized water rinse solution to neutrality, then solution is added
Enter into the sodium hydroxide solution of 0.5ml/L, mixing, afterwards ultrasound 0.5h, obtained graphene under 800W Probe Ultrasonic Searching instrument
It is stored in sodium hydroxide solution, the transmission electron microscope picture (TEM) for the graphene that the present embodiment is prepared is as shown in figure 8, by scheming
It can be seen that the graphene sheet layer prepared is big, the number of plies is few.
Embodiment 9
（1）The preparation of intercalated graphite：By graphite：Hydrogen peroxide：Proportioning=1g of sulfuric acid:10ml:Hydrogen peroxide is first added in sulphur by 30ml
In acid, mixing, add graphite, which is uniformly mixed in 15 DEG C of water-baths, is then obtained in 15 DEG C of stirred in water bath reaction 1h
To mixed solution A；It takes out mixed solution A to be added dropwise in deionized water and keep 10 DEG C of water temperature, solution is stored in ice
In case, preservation 12h obtains intercalated graphite solution at 15 DEG C.
（2）The preparation of graphene：Step（1）In intercalated graphite solution deionized water and dilute hydrochloric acid（1mol/L）It hands over
For cleaning solution respectively three times, and addition is 100ml every time, then through deionized water rinse solution to neutrality, then solution is added
Enter into the sodium hydroxide solution of 10ml/L, mixing, afterwards the ultrasound 1h under 200W Probe Ultrasonic Searching instrument, obtained graphene storage
In sodium hydroxide solution, the transmission electron microscope picture (TEM) for the graphene that the present embodiment is prepared as shown in Figure 10, can be with by figure
Find out that the graphene sheet layer of preparation is big, the number of plies is few.
Embodiment 10
（1）The preparation of intercalated graphite：By graphite：Potassium permanganate：Proportioning=0.5g of sulfuric acid:0.5g:30ml, potassium permanganate is first
It adds in sulfuric acid, mixing, adds graphite, which is uniformly mixed in 0 DEG C of water-bath, is then reacted in 0 DEG C of stirred in water bath
1h obtains mixed solution A；It takes out mixed solution A to be added dropwise in deionized water and keep 10 DEG C of water temperature, solution is stored
In refrigerator, preserved at 15 DEG C and obtain intercalated graphite solution for 24 hours.
（2）The preparation of graphene：Step（1）In intercalated graphite solution deionized water and dilute hydrochloric acid（1mol/L）It hands over
For cleaning solution respectively three times, then through deionized water rinse solution to neutrality, then solution is added to the sodium hydroxide of 10ml/L
In solution, mixing, ultrasound 1h, obtained graphene are stored in sodium hydroxide solution under 200W Probe Ultrasonic Searching instrument afterwards, this
The transmission electron microscope picture (TEM) for the graphene that embodiment is prepared as shown in figure 11, the graphene film prepared as seen from the figure
Layer is big, and the number of plies is few.
Claims (7)
1. a kind of preparation method of graphene, which is characterized in that specifically comprise the following steps：
（1）The preparation of intercalated graphite：By graphite：Oxidant：The proportioning of strong acid is 0.5 ~ 3g:0.5~3g:The ratio of 20 ~ 120ml,
Oxidant is charged first to mixing in strong acid, graphite is added and is uniformly mixed in 0 ~ 15 DEG C of water-bath, then in 0 ~ 15 DEG C of water-bath
In be stirred to react 0.5 ~ 3h and obtain mixed solution A；Mixed solution A is taken out to be added dropwise in deionized water and water temperature is kept to be less than 15
DEG C, then by mixed solution A and hydrogen peroxide volume ratio be 5:1 ratio adds in the hydrogen peroxide that mass percent concentration is 37%
Solution stirs 5 ~ 20min, water temperature less than keep 1 under conditions of 15 DEG C ~ for 24 hours, can obtain intercalated graphite solution；
（2）The preparation of graphene：Step（1）In intercalated graphite solution deionized water with dilute hydrochloric acid to replace cleaning solution each
Three times, then through deionized water rinse solution to neutrality, solution is then added to mixing in aqueous slkali, is surpassed afterwards under Ultrasound Instrument
Sound disperses 0.5 ~ 3h and obtains graphene.
2. the preparation method of graphene according to claim 1, it is characterised in that：Step（1）In oxidant for iron chloride,
One kind in potassium permanganate, hydrogen peroxide, chloric acid, hypochlorous acid, perchloric acid, nitric acid, potassium bichromate, sodium hypochlorite.
3. the preparation method of graphene according to claim 2, it is characterised in that：Work as step（1）In oxidant be dioxygen
During water, graphite is first added to mixing in hydrogen peroxide, adds strong acid.
4. the preparation method of graphene according to claim 1 or claim 2, it is characterised in that：Step（1）In strong acid for sulfuric acid,
Nitric acid or the mixture for the two.
5. the preparation method of graphene according to claim 1, it is characterised in that：Step（2）In aqueous slkali be hydroxide
The mixture of one or both of sodium solution, potassium hydroxide solution, concentration are 0.5 ~ 10mol/L；The concentration of dilute hydrochloric acid is
1mol/L。
6. the preparation method of graphene according to claim 1, it is characterised in that：Step（2）The power of middle Ultrasound Instrument is 200
~800W。
7. the preparation method of graphene according to claim 1, it is characterised in that：Step（2）Obtained graphene can be direct
It is stored in aqueous slkali or is centrifuged, be freeze-dried or dry to obtain graphene powder.
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| CN103641104A (en) * | 2013-11-22 | 2014-03-19 | 简玉君 | Preparation method of graphene |
| CN104998266A (en) * | 2015-06-30 | 2015-10-28 | 浙江师范大学 | Preparation and application of magnetic graphene oxide compound |
| CN103910354B (en) * | 2014-03-25 | 2017-01-11 | 安徽百特新材料科技有限公司 | Method for preparing graphene through large-scale aqueous phase |
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| CN103641104A (en) * | 2013-11-22 | 2014-03-19 | 简玉君 | Preparation method of graphene |
| CN103910354B (en) * | 2014-03-25 | 2017-01-11 | 安徽百特新材料科技有限公司 | Method for preparing graphene through large-scale aqueous phase |
| CN104998266A (en) * | 2015-06-30 | 2015-10-28 | 浙江师范大学 | Preparation and application of magnetic graphene oxide compound |
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