CN106629673B - A kind of preparation method of graphene oxide - Google Patents
A kind of preparation method of graphene oxide Download PDFInfo
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- CN106629673B CN106629673B CN201610822040.3A CN201610822040A CN106629673B CN 106629673 B CN106629673 B CN 106629673B CN 201610822040 A CN201610822040 A CN 201610822040A CN 106629673 B CN106629673 B CN 106629673B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 67
- 239000010439 graphite Substances 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 34
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 55
- 239000012286 potassium permanganate Substances 0.000 claims description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000006193 liquid solution Substances 0.000 claims description 10
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 9
- 230000002687 intercalation Effects 0.000 claims description 9
- 238000009830 intercalation Methods 0.000 claims description 9
- 235000010344 sodium nitrate Nutrition 0.000 claims description 9
- 239000004317 sodium nitrate Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 230000009514 concussion Effects 0.000 claims description 5
- 238000002474 experimental method Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011877 solvent mixture Substances 0.000 claims description 3
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 2
- 239000000243 solution Substances 0.000 abstract description 30
- 239000002253 acid Substances 0.000 abstract description 4
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 230000010355 oscillation Effects 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 alkene compound Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to technical field of graphene preparation, in particular to a kind of preparation method of graphene oxide.It the described method comprises the following steps: (1) using common graphite powder as raw material, the graphite suspension containing thin graphite flake layer is made using liquid phase stripping method；(2) it filters and dry, obtains graphite flake powder；(3) oxidant is added, carries out oxidation reaction；(4) graphite oxide is formed at 20-40 DEG C by aoxidizing bold and vigorous ice method；(5) graphite oxide is cleaned and is dried；Then deionized water or organic solvent is added, and is ultrasonically treated, the graphene oxide dispersion containing graphene oxide is obtained.The present invention is reoxidized using ultrasonic oscillation removing graphite and prepares graphene oxide, and obtained graphene oxide can be dispersed in water, acid solution, alkaline solution or organic solution, form evenly dispersed graphene oxide.This method has many advantages, such as that simple process, success rate are high, operating condition is easily controllable.
Description
Technical field
The invention belongs to technical field of graphene preparation, in particular to a kind of preparation method of graphene oxide.
Background technique
Graphene (Graphene) is a kind of plane for forming hexangle type in honeycomb lattice with sp2 hybridized orbit by carbon atom
Film, the two-dimensional material of only one carbon atom thickness.Graphene has always been considered as the structure of assuming that property, can not individually stablize
In the presence of, until 2004, Univ Manchester UK physicist An Deliehaimu and Constantine's Nuo Woxiao love, at
Function single-layer graphene is just separated and observes for the first time using micromechanics stripping method from graphite in an experiment, to confirm
It also because of " in the initiative experiment of two-dimensional graphene material ", can obtain jointly Nobel in 2010 with individualism, two people
Physics Prize.
It is but also most hard nano material that graphene, which is currently most thin in the world, it is almost fully transparent, only absorption
2.3% light；Thermal coefficient is up to 5300W/mK, is higher than carbon nanotube and diamond, its electron mobility is more than under room temperature
15000cm2/ Vs, but it is higher than carbon nanotubes or silicon crystal, and resistivity about 10-6Ω cm, it is lower than copper or silver, it is mesh
The smallest material of resistivity on previous existence.Because its resistivity is extremely low, the speed that electronics is run is exceedingly fast, therefore is expected to can be used to send out
Put on display thinner, conductive speed electronic component or transistor of new generation faster.Since graphene is substantially a kind of transparent, good
Conductor, be also adapted to manufacture transparent touch screen, tabula rasa, even solar battery.
Graphene oxide is product of the powdered graphite after chemical oxidation and delamination, and graphene oxide is single atom
Layer, can on lateral dimension from tens nanometers to some tens of pm, therefore, the general chemistry of construct trans and material science
Typical size.Graphene oxide can be considered as a kind of flexible material of non-traditional form, with polymer, colloid, film
Characteristic.Since graphene oxide has derivative carboxyl at lamella edge, there is phenolic hydroxyl group and epoxy group, conjugation in the plane
Network receives serious functionalization, and it is to prepare graphite that graphene oxide, which has regulatable surface-active, electrical property and optical characteristics,
Important intermediate compound during alkene compound and graphene functionalized.It is extensive that graphene oxide is prepared with graphite powder
The starting point of graphene is prepared, and realizes one of the effective ways that graphene is largely prepared.
Currently, relatively conventional graphene oxide preparation method mainly has: Brodie method, Staudenmaier method,
Hummers method.
Chinese patent application CN101817516A obtains stone using separation after solid particle auxiliary mechanical stripping carbon materials
Black alkene or graphene oxide, but be not using liquid phase householder method and to remove solid particle difficulty.
Then graphite powder, sodium nitrate low-temperature oxidation in concentrated sulfuric acid are added high Chinese patent application CN105399084A
Potassium manganate further aoxidizes intercalation under medium temperature, and finally reaction obtains graphene oxide at high temperature, and this method is needed in high temperature
Lower reaction, increases control difficulty.
Chinese patent application CN104876219A is based on Hummers method under 10-30 DEG C of room temperature, mixes to graphite oxide
Hydrogen peroxide solution is added in liquid, obtains graphene oxide water solution under ultrasonic wave effect, but the graphite that this method first carries out
Oxidation step, thus it is higher to the quality requirements of graphite raw material, increase the manufacturing cost of graphene oxide.
Although in the actual operation process, the above method can successfully prepare graphene oxide, the above method
For the more demanding of raw graphite, generally require using the crystalline flake graphite raw material for being easier to generation oxidation reaction, and if
Using thicker, biggish graphite powder, be difficult that the graphene oxide of high-quality is made, thus improve the manufacture of graphene oxide at
This.In addition, above-mentioned preparation method in preparing graphite oxide step, generally requires to carry out under temperature above room temperature, and need
Strict control reaction temperature will lead to preparation failure once temperature control is bad.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of improved graphene oxide, and the biggish graphite of particle can be used
Powder, and without being heated at high temperature in preparing graphite oxide step, it is easily prepared.
To achieve the goals above, the present invention provides the following technical scheme that
The present invention provides a kind of preparation method of graphene oxide, comprising the following steps:
(1) it prepares graphite suspension: using common graphite powder as raw material, being made using liquid phase stripping method and contain thin graphite flake layer
Graphite suspension；
(2) it prepares graphite flake powder: to graphite suspension made from step (1), being filtered and dry, obtain graphite
Flake powder；
(3) intercalation: solvent being added into graphite flake powder made from step (2), carries out intercalation；
(4) it prepares graphite oxide: to step (3) acquired solution, forming oxidation at 20 DEG C -40 DEG C by aoxidizing bold and vigorous ice method
Graphite；
(5) it cleans and is ultrasonically treated: graphite oxide made from step (4) is cleaned and dried；Then be added go from
Sub- water or organic solvent, and be ultrasonically treated, obtain the graphene oxide dispersion containing graphene oxide.
In the step (1), the common graphite powder is selected from crystalline graphite powder, expansible graphite powder or microcrystal graphite
Powder.
In the step (1), the liquid phase stripping method detailed process are as follows: common graphite powder, institute are added into liquid solution
The weight for stating common graphite powder is the 0.1-2% of liquid solution weight, in 20 DEG C -50 DEG C of temperature and under confined conditions, with big
It is shaken or is ground in the ultrasonic wave for being equal to 80 watts of power, concussion or milling time are 1-12 hours.
The liquid solution is selected from one of following mixed liquor:
Deionized water and acetone mixture, wherein acetone is 70-90wt%；Or
Acetone and alcohol mixeding liquid, wherein acetone is 70-90wt%；Or
Acetone and N- methyl-prop network alkanone mixed liquor, wherein acetone is 10-30wt%.
In the filtration step of the step (2), using ordinary filter paper or membrane filtration, the ordinary filter paper is experiment
Qualitative or quantitative filter paper.
In the drying steps of the step (2), drying temperature is 40 DEG C -90 DEG C, and the time is 6-12 hours.
In the step (3), graphite flake powder and solvent mixture are placed in ice bath with magnetic agitation 2-4 hours,
Keeping temperature is to be sufficiently mixed graphite flake powder with solvent between 0 DEG C -5 DEG C.
In the step (3), the intercalation solvent is the combination of sodium nitrate and the concentrated sulfuric acid, or is concentrated nitric acid and dense
The combination of sulfuric acid.
The weight ratio of graphite flake powder and sodium nitrate and the concentrated sulfuric acid is 2:1:80-100；Graphite flake powder and dense nitre
The weight ratio of acid and the concentrated sulfuric acid is 1:15-20:55-70.
In the step (4), described aoxidize sprinkles ice method detailed process are as follows:
Under condition of ice bath, continue whipping step (3) acquired solution, be slowly added to potassium permanganate, the potassium permanganate with
The weight ratio of the common graphite powder is 3:1, and during potassium permanganate is added, solution temperature is not higher than 10 DEG C；To permanganic acid
Potassium starts timing after being all added, and is persistently stirred to react under ice bath 0.5-2 hours；At this point, solution is blackish green；By beaker
It moves in 20 DEG C of -40 DEG C of tepidariums, is stirred to react 6-8 hours；
Then, it is added at one time potassium permanganate, the weight ratio of the potassium permanganate and the common graphite powder is 3:1,
It is stirred in 20 DEG C of -40 DEG C of tepidariums 8-12 hours；After reaction product is cooled to room temperature, sprinkles and containing 5-30% hydrogen peroxide
It on the ice cube of aqueous solution, and stirs, in whipping process, then hydrogenperoxide steam generator is added dropwise, solution can become bright orange from reddish brown
Color solution obtains graphite oxide in ie in solution.
In the step (5), cleaning operation is carried out using deionized water.
The organic solvent is N- methyl-prop network alkanone NMP, dimethylformamide DMF or dimethyl sulfoxide DMSO.
Compared with prior art, the beneficial effects of the present invention are:
During the present invention is for graphene oxide is prepared using chemical oxidization method at present, powdered graphite is thicker, prepares
Cheng Wendu control is difficult, is easier to the technical issues of failure occurs, and under the premise of preparatory liquid phase removes graphite, avoids to product
It is heated at high temperature, reduces preparation difficulty, improve success rate.There is this method simple process, at low cost, operating condition to be easy to control
The advantages that processed.The present invention prepares graphene oxide using liquid phase lift-off technology assistant reinforcement at 20-40 DEG C, eliminates
High-temperature step in Hummers method improves production graphene oxide yield rate and quality.
Detailed description of the invention
Fig. 1 present invention prepares the flow chart of the method for graphene oxide；
The raman spectrum for the graphene oxide that Fig. 2 is prepared using crystalline graphite powder
The transmission electron microscope shape appearance figure for the graphene oxide that Fig. 3 is prepared using crystalline graphite powder；
The transmission electron microscope shape appearance figure for the graphene oxide that Fig. 4 is prepared using expansible graphite powder；
The transmission electron microscope shape appearance figure for the graphene oxide that Fig. 5 is prepared using microlite ink powder.
Specific embodiment
The present invention will be further described below in conjunction with the embodiments.
A kind of preparation method of graphene oxide of the invention, comprising the following steps:
(1) it prepares graphite suspension: using common graphite powder as raw material, being made using liquid phase stripping method and contain thin graphite flake layer
Graphite suspension.
The common graphite powder is selected from crystalline graphite powder, expansible graphite powder or microcrystal graphite powder.
The liquid phase stripping method detailed process are as follows: common graphite powder is added into liquid solution, common graphite powder is added
Weight is the 0.1-2% of liquid solution weight.Preferably, the weight of common graphite powder is the 0.5-2% of liquid solution weight.?
20 DEG C -50 DEG C of temperature and under confined conditions is shaken or is ground to be more than or equal to the ultrasonic wave of 80 watts of power, concussion or
Milling time is 1-12 hours.
The liquid solution is the mixed solution for meeting any two of graphene Hansen solubility parameter theory, is preferably gone
The mixed liquor of ionized water and acetone, acetone and ethyl alcohol, acetone and N- methyl-prop network alkanone (NMP).
Deionized water and acetone mixture, wherein acetone is 70-90wt%；Or
Acetone and alcohol mixeding liquid, wherein acetone is 70-90wt%；Or
Acetone and N- methyl-prop network alkanone mixed liquor, wherein acetone is 10-30wt%.
(2) it prepares graphite flake powder: to graphite suspension made from step (1), being filtered and dry, obtain graphite
Flake powder.
Using ordinary filter paper, as experiment the filtering of qualitative perhaps quantitative filter paper or using filter membrane such as miillpore filter into
Row filtering.
Drying temperature is 40 DEG C -90 DEG C, and the time is 6-12 hours.
(3) intercalation: solvent being added into graphite flake powder made from step (2), carries out intercalation；By graphite
Flake powder and solvent mixture are placed in ice bath with magnetic agitation 2-4 hours, are maintained the temperature between 0 DEG C -5 DEG C, are made graphite
Flake powder is sufficiently mixed with solvent.
The intercalation solvent is the combination of sodium nitrate and the concentrated sulfuric acid, or the combination for concentrated nitric acid and the concentrated sulfuric acid；
The weight ratio of graphite flake powder and sodium nitrate and the concentrated sulfuric acid is 2:1:80-100, graphite flake powder and dense nitre
The weight ratio of acid and the concentrated sulfuric acid is 1:15-20:55-70.
(4) it prepares graphite oxide: to step (3) acquired solution, forming oxidation stone at 20-40 DEG C by aoxidizing bold and vigorous ice method
Ink；
It aoxidizes bold and vigorous ice method and forms graphene oxide at 20 DEG C -40 DEG C, eliminate the hot stage in conventional H ummers method
It (being higher than 80 DEG C), only need to be by the way that a potassium permanganate be simply added twice.
Described aoxidize sprinkles ice method detailed process are as follows:
Under condition of ice bath, continue whipping step (3) acquired solution, be slowly added to potassium permanganate, the potassium permanganate with
The weight ratio of the common graphite powder is 3:1, is guaranteed during potassium permanganate is added, and solution temperature is not higher than 10 DEG C；To height
Potassium manganate starts timing after being all added, and is persistently stirred to react under ice bath 0.5-2 hours.At this point, solution is blackish green；It will
Beaker moves in 20 DEG C of -40 DEG C of tepidariums, is stirred to react 6-8 hours.
Then, potassium permanganate, the potassium permanganate, the weight of the potassium permanganate and the common graphite powder are added at one time
Amount is stirred for 8-12 hours than being 3:1 in 20 DEG C of -40 DEG C of tepidariums.After reaction product is cooled to room temperature, sprinkles and containing 5-
On the ice cube of 30% aqueous hydrogen peroxide solution.In whipping process, then hydrogenperoxide steam generator is added dropwise, solution can become from reddish brown
Bright yellow solution obtains graphite oxide in ie in solution.
(5) it cleans and is ultrasonically treated: graphite oxide made from step (4) is cleaned and dried；Then be added go from
Sub- water or organic solvent, and be ultrasonically treated, obtain the graphene oxide dispersion containing graphene oxide.
In step (5), cleaning operation is carried out using deionized water.
The organic solvent is N- methyl-prop network alkanone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO)
Deng.
Embodiment 1
Using crystalline graphite powder as primary raw material, acetone and water preparation removing graphite powder are chosen.160mL acetone is taken, 40mL is gone
Ionized water.2g crystalline graphite powder is taken, is added in mixed liquor, under confined conditions 80 watts of power ultrasonic vibrations, temperature is kept to be not higher than
50 DEG C, the concussion time is 6 hours.
After the completion, filter paper filters, then 6 hours dry, the acquirement graphite flake powder at 40 DEG C.
1g graphite flake powder is taken, 0.5g sodium nitrate is added, the 43g concentrated sulfuric acid places it in small with magnetic agitation 3 in ice bath
When, keeping temperature is 0 DEG C.
Under condition of ice bath and continue agitating solution, be slowly added to 3g potassium permanganate, guarantees that potassium permanganate mistake is being added
Cheng Zhong, solution temperature are not higher than 10 DEG C.Start timing after being all added to potassium permanganate, is persistently stirred to react 2 under ice bath
Hour.At this point, solution is blackish green.Beaker is moved in 20 DEG C of tepidariums, is stirred to react 7 hours.3g high is added in property again
Potassium manganate is stirred for 12 hours in 20 DEG C of tepidariums.After reaction product is cooled to room temperature, sprinkles and containing 30% hydrogen peroxide
On the ice cube of aqueous solution.In whipping process, then hydrogenperoxide steam generator being added dropwise, solution can become bright yellow solution from reddish brown,
Graphite oxide is obtained in ie in solution.
It is 12 hours dry at 60 DEG C or less after collecting solid by being cleaned multiple times, obtain graphene oxide powder.It weighs
Deionized water is added in certain powder, and graphene oxide dispersion can be obtained in ultrasonic vibration.
Embodiment 2
Using expansible graphite powder as primary raw material, with acetone and ethyl alcohol preparation removing graphite powder.180mL acetone, 20mL second
Alcohol, 1g expansible graphite powder, ultrasonic vibration, holding temperature are not higher than 50 DEG C to mixed liquor in confined conditions after mixing, shake
Swinging the time is 6 hours.
After the completion, filter paper filters, then 6 hours dry, the acquirement graphite flake powder at 50 DEG C.
The 60g concentrated sulfuric acid is added in 1g graphite flake powder, places it in magnetic agitation 3 hours in ice bath, slowly drips
Enter 18g concentrated nitric acid, keeping temperature is 4 DEG C, is stirred 40 minutes.
Under condition of ice bath and continue agitating solution, be slowly added to 3g potassium permanganate, guarantees that potassium permanganate mistake is being added
Cheng Zhong, solution temperature is not above 10 DEG C.Start timing after being all added to potassium permanganate, is persistently stirred to react under ice bath
2 hours.Beaker is moved in 31 DEG C of tepidariums, is stirred to react 7 hours.3g potassium permanganate is added in property again, in 31 DEG C of warm water
It is stirred in bath 12 hours.After reaction product is cooled to room temperature, sprinkle on the ice cube containing 10% aqueous hydrogen peroxide solution.It stirs
During mixing, then hydrogenperoxide steam generator is added dropwise, solution can become bright yellow solution from reddish brown, and oxidation stone is obtained in ie in solution
Ink.
By being cleaned multiple times, after collecting solid, 12 hours dry at 60 DEG C or less, this is graphene oxide powder.It weighs
Deionized water is added in certain powder, and graphene oxide dispersion can be obtained in ultrasonic vibration.
Embodiment 3
Raw material is wanted based on microlite ink powder, chooses acetone and N- methyl-prop network alkanone (NMP) preparation removing graphite powder.It takes
20mL acetone, 80mLN- methyl-prop network alkanone (NMP).2g microlite ink powder is taken, is added in mixed liquor, under confined conditions ultrasound shake
It swings, keeps temperature to be not higher than 50 DEG C, the concussion time is 6 hours.
After the completion, filter paper filters, then 6 hours dry, the acquirement desciccate at 50 DEG C.
1g desciccate is taken, 0.5g sodium nitrate is added, the 43g concentrated sulfuric acid is placed it in magnetic agitation 3 hours in ice bath,
Keeping temperature is 5 DEG C.
Under condition of ice bath and continue agitating solution, be slowly added to 3g potassium permanganate, guarantees that potassium permanganate mistake is being added
Cheng Zhong, solution temperature is not above 10 DEG C.Start timing after being all added to potassium permanganate, is persistently stirred to react under ice bath
2 hours.Beaker is moved in 40 DEG C of tepidariums, is stirred to react 7 hours.3g potassium permanganate is added in property again, in 40 DEG C of warm water
It is stirred in bath 12 hours.After reaction product is cooled to room temperature, sprinkle on the ice cube containing 20% aqueous hydrogen peroxide solution.It stirs
During mixing, then hydrogenperoxide steam generator is added dropwise, obtains graphite oxide.
By being cleaned multiple times, after collecting solid, 12 hours dry at 60 DEG C or less, this is graphene oxide powder.It weighs
Deionized water is added in certain powder, and graphene oxide dispersion can be obtained in ultrasonic vibration.
Although describing determining embodiment, these embodiments are only used as example to occur, and are not intended to limit
The scope of the present invention.In fact, new embodiment described herein can be revised as any other form；Furthermore it is possible to not taking off
From formal different omissions, substitution and the change under spirit of the invention, carrying out embodiment described here, when falling
When entering in scope and spirit of the present invention, accessory claim and its equivalent are intended to cover such form or modification.
Claims (9)
1. a kind of preparation method of graphene oxide, it is characterised in that: method includes the following steps:
(1) it prepares graphite suspension: using common graphite powder as raw material, the stone containing thin graphite flake layer is made using liquid phase stripping method
Black suspension；
(2) it prepares graphite flake powder: to graphite suspension made from step (1), being filtered and dry, obtain graphite flake
Powder；
(3) intercalation: solvent being added into graphite flake powder made from step (2), carries out intercalation；
(4) it prepares graphite oxide: to step (3) acquired solution, forming oxidation stone at 20 DEG C -40 DEG C by aoxidizing bold and vigorous ice method
Ink；
(5) it cleans and is ultrasonically treated: graphite oxide made from step (4) is cleaned and dried；Then deionized water is added
Or organic solvent, and be ultrasonically treated, obtain the graphene oxide dispersion containing graphene oxide；
In the step (1), the liquid phase stripping method detailed process are as follows: common graphite powder is added into liquid solution, it is described general
The weight of logical graphite powder is the 0.1-2% of liquid solution weight, in 20 DEG C -50 DEG C of temperature and under confined conditions, with greater than etc.
It is shaken or is ground in the ultrasonic wave of 80 watts of power, concussion or milling time are 1-12 hours；
The liquid solution is selected from one of following mixed liquor:
Deionized water and acetone mixture, wherein acetone is 70-90wt%；Or
Acetone and alcohol mixeding liquid, wherein acetone is 70-90wt%；Or
Acetone and N- methyl-prop network alkanone mixed liquor, wherein acetone is 10-30wt%；
In the step (4), described aoxidize sprinkles ice method detailed process are as follows:
Under condition of ice bath, continue whipping step (3) acquired solution, be slowly added to potassium permanganate, the potassium permanganate with it is described
The weight ratio of common graphite powder is 3:1, and during potassium permanganate is added, solution temperature is not higher than 10 DEG C；It is complete to potassium permanganate
Portion starts timing after being added, and is persistently stirred to react under ice bath 0.5-2 hours；At this point, solution is blackish green；Beaker is moved to
In 20 DEG C of -40 DEG C of tepidariums, it is stirred to react 6-8 hours；
Then, be added at one time potassium permanganate, the weight ratio of the potassium permanganate and the common graphite powder is 3:1,20 DEG C-
It is stirred in 40 DEG C of tepidariums 8-12 hours；After reaction product is cooled to room temperature, sprinkle water-soluble containing 5-30% hydrogen peroxide
It on the ice cube of liquid, and stirs, in whipping process, then hydrogenperoxide steam generator is added dropwise, it is molten that solution can become glassy yellow from reddish brown
Liquid obtains graphite oxide in ie in solution.
2. the preparation method of graphene oxide according to claim 1, it is characterised in that: described general in the step (1)
Logical graphite powder is selected from crystalline graphite powder, expansible graphite powder or microlite ink powder.
3. the preparation method of graphene oxide according to claim 1, it is characterised in that: the filtering of the step (2) walks
In rapid, using ordinary filter paper or membrane filtration, the ordinary filter paper is the qualitative or quantitative filter paper of experiment.
4. the preparation method of graphene oxide according to claim 1, it is characterised in that: the dry step of the step (2)
In rapid, drying temperature is 40 DEG C -90 DEG C, and the time is 6-12 hours.
5. the preparation method of graphene oxide according to claim 1, it is characterised in that: in the step (3), by graphite
Flake powder and solvent mixture are placed in ice bath with magnetic agitation 2-4 hours, and keeping temperature is to make graphite between 0 DEG C -5 DEG C
Flake powder is sufficiently mixed with solvent.
6. the preparation method of graphene oxide according to claim 1, it is characterised in that: described to insert in the step (3)
Layer reaction dissolvent is the combination of sodium nitrate and the concentrated sulfuric acid, or the combination for concentrated nitric acid and the concentrated sulfuric acid.
7. the preparation method of graphene oxide according to claim 6, it is characterised in that: graphite flake powder and sodium nitrate
Weight ratio with the concentrated sulfuric acid is 2:1:80-100；The weight ratio of graphite flake powder and concentrated nitric acid and the concentrated sulfuric acid is 1:15-
20:55-70.
8. the preparation method of graphene oxide according to claim 1, it is characterised in that: in the step (5), using going
Ionized water carries out cleaning operation.
9. the preparation method of graphene oxide according to claim 1, it is characterised in that: the organic solvent is N- methyl
Third network alkanone NMP, dimethylformamide DMF or dimethyl sulfoxide DMSO.
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| CN107043104A (en) * | 2017-05-11 | 2017-08-15 | 桂林理工大学 | A kind of graphene quantum dot induces high nitrogen doped photo-reduction graphene oxide preparation method |
| CN107720739A (en) * | 2017-09-30 | 2018-02-23 | 湖南国盛石墨科技有限公司 | The preparation method of micro crystal graphite alkene |
| CN107867685A (en) * | 2017-10-18 | 2018-04-03 | 复旦大学 | A kind of preparation method of the native graphite heat dissipation film of high heat conductance |
| CN107697911B (en) * | 2017-10-18 | 2021-12-28 | 复旦大学 | Method for preparing natural graphite heat dissipation film from graphite oxide |
| CN110272039A (en) * | 2018-03-15 | 2019-09-24 | 中国科学院宁波材料技术与工程研究所 | A kind of high-concentration biological base two-dimensional material dispersion liquid, preparation method and application |
| CN110265542B (en) * | 2019-07-09 | 2021-02-09 | 山东光韵智能科技有限公司 | High-energy light absorption and conversion material for radiation protection in high-risk area and manufacturing method thereof |
| CN110980717A (en) * | 2019-10-29 | 2020-04-10 | 广东墨睿科技有限公司 | Method for preparing graphene oxide by using vermicular graphite |
| CN111704126A (en) * | 2020-05-14 | 2020-09-25 | 上海大学 | Reduction method of graphene oxide |
| CN112479196A (en) * | 2020-06-11 | 2021-03-12 | 中科远方(北京)科技有限公司 | Graphene oxide and preparation method thereof |
| CN112408371B (en) * | 2020-10-30 | 2022-06-14 | 宁波石墨烯创新中心有限公司 | Graphene heat-conducting film, preparation method thereof and electronic equipment |
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