CN113683084A - Preparation method of functionalized few-layer graphene - Google Patents
Preparation method of functionalized few-layer graphene Download PDFInfo
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- CN113683084A CN113683084A CN202110971908.7A CN202110971908A CN113683084A CN 113683084 A CN113683084 A CN 113683084A CN 202110971908 A CN202110971908 A CN 202110971908A CN 113683084 A CN113683084 A CN 113683084A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 36
- 230000009471 action Effects 0.000 claims abstract description 28
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 25
- 239000010439 graphite Substances 0.000 claims abstract description 25
- 238000009830 intercalation Methods 0.000 claims abstract description 17
- 230000002687 intercalation Effects 0.000 claims abstract description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- 239000000138 intercalating agent Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 38
- 238000005457 optimization Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000002045 lasting effect Effects 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
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
Abstract
The invention relates to a preparation method of functionalized few-layer graphene, which comprises the following steps: step 1), mixing graphite and an intercalation reagent, and transferring the mixture to a high-speed machine for a first-stage action to obtain a mixture; and 2) adding a solvent into the mixture obtained in the first step to continue the second stage action, and separating and washing after the second stage action is finished to obtain the functionalized oligolayer graphene with the surface containing the functional group. The thickness and the sheet diameter of the product obtained by the preparation method disclosed by the invention are controllable, the process is simple, the large-scale production is easy, and the prepared product has high conductivity and few defects. In the action process, the intercalation and mechanical stripping of the intercalating agent are simultaneously carried out, so that the preparation of the few-layer graphene is accelerated; meanwhile, intercalation and introduction of functional groups are carried out synchronously, which is beneficial to dispersion of the few-layer graphene.
Description
Technical Field
The invention relates to the technical field of carbon nano materials, in particular to a preparation method of functionalized few-layer graphene.
Background
The functionalized few-layer graphene has the advantages of graphene and graphene oxide, namely, high specific surface area, adjustable lamella thickness, high conductivity, good solution dispersibility and processability, and has wide application prospects in the fields of energy storage and conversion, environment, catalysis and the like. Therefore, the preparation of functionalized oligo-layer graphene attracts academic and industrial concerns.
Currently, methods for preparing graphene or few-layer graphene mainly include the following steps: (1) the oxidation-reduction method is typically represented by a Hummers method, and adopts substances with strong oxidizing property (such as potassium permanganate, potassium nitrate, concentrated sulfuric acid, hydrogen peroxide and the like) to intercalate graphite and strip the graphite to prepare graphene oxide, and then the graphene oxide is prepared by chemical or thermal reduction, so that the method has the advantages of simple operation and suitability for scale preparation, but the obtained product has the defects of poor conductivity and multiple defects, a large amount of strong corrosive acid and oxidant are used in the preparation process, waste acid and heavy metal ions are generated, the environment is polluted, and the post-treatment is complex; (2) the ultrasonic stripping method is characterized in that the graphene or the few-layer graphene is obtained by carrying out ultrasonic treatment on graphite and a surfactant in an organic solvent, and the product obtained by the method has the advantages of high conductivity and few defects, but has the defect of low yield; (3) the graphene prepared by the Chemical Vapor Deposition (CVD) method has high quality, good conductivity and few defects, has certain advantages in the field of electronics and semiconductor industry, but has the defects of difficult process control, high cost and low yield. Therefore, an efficient and simple method for preparing few-layer graphene is urgently developed.
Disclosure of Invention
The invention aims to solve the technical problems and provide a preparation method of functionalized few-layer graphene.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of functionalized few-layer graphene comprises the following steps:
step 1), mixing graphite and an intercalation reagent, and transferring the mixture to a high-speed machine for a first-stage action to obtain a mixture;
and 2) adding a solvent into the mixture obtained in the first step to continue the second stage action, and separating and washing after the second stage action is finished to obtain the functionalized oligolayer graphene with the surface containing the functional group.
As a further optimization of the preparation method of the functionalized few-layer graphene, the graphite is one of crystalline flake graphite, oriented cracked graphite, expanded graphite or natural graphite.
As a further optimization of the preparation method of the functionalized few-layer graphene, the intercalation reagent in the first step is one or more of concentrated sulfuric acid, concentrated nitric acid, concentrated phosphoric acid and hydrogen peroxide.
As a further optimization of the preparation method of the functionalized few-layer graphene, the mass ratio of the graphite in the step one to the graphite in the intercalation reagent is 1-30%, and the mass ratio of the intercalation reagent is more than 70%.
As a further optimization of the preparation method of the functionalized few-layer graphene, the high-speed machine in the first step is one of a stirrer, a shearing machine, a ball mill, a grinding machine or a dispersing machine.
As a further optimization of the preparation method of the functionalized few-layer graphene, the first stage of the step I has the action time of 30min-12h, the temperature of-20-50 ℃ and the speed of 100-500 rpm.
As a further optimization of the preparation method of the functionalized few-layer graphene, the solvent in the second step is one or more of deionized water, ethanol and isopropanol.
As a further optimization of the preparation method of the functionalized few-layer graphene, the mass ratio of the solvent in the second step is 50-90%;
as a further optimization of the preparation method of the functionalized few-layer graphene, the second stage of the step two is carried out for 20min-24h at the speed of 500-10000rpm and at the temperature of 0-80 ℃.
As a further optimization of the preparation method of the functionalized few-layer graphene, the separation method in the second step is one or more of centrifugation, spray drying, suction filtration and freeze drying.
Advantageous effects
The preparation method of the functionalized few-layer graphene disclosed by the invention has the following advantages:
firstly, the raw materials are cheap and easy to obtain, and the post-treatment process is easy. The method is basically a one-pot reaction in the process of preparing the few-layer graphene, raw materials (graphite and intercalation reagent) are added into an action high-speed machine, only action parameters are controlled, and a certain amount of solvent is added, and the adopted intercalation reagent does not contain heavy metal ions, is environment-friendly, has good water solubility and is easy to remove.
The thickness and the sheet diameter of the product obtained by the preparation method disclosed by the invention are controllable, the process is simple, the large-scale production is easy, and the prepared few-layer graphene has relatively complete inner layer structure, few defects and higher conductivity. In the action process, the intercalation and mechanical stripping of the intercalating agent are simultaneously carried out, so that the preparation of the few-layer graphene is accelerated; meanwhile, intercalation and introduction of functional groups are carried out synchronously, which is beneficial to dispersion of the few-layer graphene.
Drawings
FIG. 1 is a scanning electron microscope image of few-layer graphene obtained in example 1 of the present invention;
FIG. 2 is a thermogravimetric analysis chart of the few-layer graphene obtained in example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of the few-layer graphene obtained in example 2 of the present invention;
FIG. 4 is an XRD pattern of the graphene oligo-layer powder obtained in example 3 of the present invention;
fig. 5 is a raman spectrum of the few-layer graphene obtained in example 3 of the present invention.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Example 1
In the embodiment, crystalline flake graphite is used as a raw material, concentrated sulfuric acid is used as an intercalation agent, and a high-speed shearing machine is used as an acting machine.
The preparation method comprises the following specific steps: weighing 1500g of concentrated sulfuric acid, weighing 30g of crystalline flake graphite, adding, stirring and mixing uniformly, transferring into a high-speed shearing machine, performing a first-stage action at a rotating speed of 100rpm, and maintaining the system temperature at 0 ℃ in the process for 1 h. Then, on the basis thereof, 5000kg of deionized water was added and the second stage action was carried out at 2000rpm, the action lasting for 5 hours. And finally, carrying out centrifugal separation at 2500rpm, washing and drying to obtain 45g of the oligolayer graphene with the surface containing the functional group, wherein a scanning electron microscope image of the obtained oligolayer graphene is shown in figure 1, and the obtained product is lamellar and has no obvious agglomeration phenomenon.
The method comprises the steps of preparing the few-layer graphene by adjusting the ratio of raw materials to an intercalating agent, the action temperature and the action time of a high-speed shearing machine, and is shown in table 1.
Table 1:
example 2
Weighing 40g of expanded graphite and 3000g of concentrated phosphoric acid, stirring and mixing uniformly, transferring into a ball mill, and performing a first-stage action at the rotating speed of 150rpm at room temperature for 1 h. Next, 6000kg of deionized water was added and the second stage action was carried out at room temperature and continued at 3000rpm for 10 h. Finally, the mixture is centrifugally separated at 1500rpm, washed and dried to obtain 38g of the oligolamellar graphene, and the conductivity of the obtained oligolamellar graphene is 6.5 to 102And the thermogravimetric analysis chart is shown in fig. 2, it can be seen that the obtained oligo-layer graphene has functional groups on the surface, the content of which is about 30%, and the functional groups are helpful for the dispersion of the product in water or other solvents; as can be seen from a scanning electron microscope image (as shown in FIG. 3), the product is in a sheet shape, the surface of the product has certain wrinkles, and the product does not have an agglomeration phenomenon, and the side surface of the product shows that the few-layer graphene prepared by the method has good processability.
Example 3
Weighing 2500g (mass ratio of 2:1) of concentrated sulfuric acid and hydrogen peroxide, weighing 35g of natural graphite, adding, stirring and mixing uniformly, transferring to a high-speed stirrer, performing a first-stage action at a rotating speed of 150rpm, and maintaining the system temperature at 0 ℃ during the first-stage action for 1.5 h. Then, on the basis, 4000kg of deionized water is added to start the second stage action, the action is firstly continued for 2 hours at the rotating speed of 300rpm, and then the action is continued for 3 hours at the rotating speed of 4000 rpm. And finally, carrying out suction filtration, washing and drying to obtain 55g of the oligo-layer graphene with the surface containing functional groups and the conductivity of 6.5 x 10. The XRD pattern of the obtained few-layer graphene is shown in figure 4, the peak which appears near 12 degrees is mainly caused by the effect of the intercalation agent on graphite, the interlayer spacing is increased due to the functional group introduced on the surface, and a relatively wide peak appears near 25 degrees, which is close to the interlayer spacing of graphite and belongs to the inner lamella of the few-layer graphene which is not functionalized, which indicates that the few-layer graphene is functionalized by the surface layerThe structure of the graphene is that the interior of the graphene is provided with a graphite sheet layer, so that the graphene is endowed with good processability, and good conductivity is ensured; the Raman spectrum is shown in FIG. 5, 1680cm-1The near peak is the characteristic peak of graphitization and is in 1350cm-1The nearby peaks are due to defects and heteroatoms, which indicates that the use of the intercalating agent indeed introduces functional groups on the surface of the oligo-layer graphene.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. A preparation method of functionalized few-layer graphene is characterized by comprising the following steps: the method comprises the following steps:
step 1), mixing graphite and an intercalation reagent, and transferring the mixture to a high-speed machine for a first-stage action to obtain a mixture;
and 2) adding a solvent into the mixture obtained in the first step to continue the second stage action, and separating and washing after the second stage action is finished to obtain the functionalized oligolayer graphene with the surface containing the functional group.
2. The method of claim 1, wherein the method comprises: the graphite is one of crystalline flake graphite, oriented cracked graphite, expanded graphite or natural graphite.
3. The method of claim 1, wherein the method comprises: the intercalation reagent in the step one is one or more of concentrated sulfuric acid, concentrated nitric acid, concentrated phosphoric acid and hydrogen peroxide.
4. The method of claim 1, wherein the method comprises: the mass ratio of the graphite in the step one to the graphite in the intercalation reagent is 1-30%, and the mass ratio of the intercalation reagent is more than 70%.
5. The method of claim 1, wherein the method comprises: the high-speed machine in the step one is one of a stirrer, a shearing machine, a ball mill, a grinding machine or a dispersion machine.
6. The method of claim 1, wherein the method comprises: the first stage of the first step has the action time of 30min-12h, the temperature of-20-50 ℃, and the speed of 100-500 rpm.
7. The method of claim 1, wherein the method comprises: the solvent in the second step is one or more of deionized water, ethanol and isopropanol.
8. The method of claim 1 or 7, wherein the functionalized oligo-layer graphene is prepared by: and the mass ratio of the solvent in the step two is 50-90%.
9. The method of claim 1, wherein the method comprises: the second stage of the second step has the action time of 20min-24h, the speed of 500-10000rpm and the temperature of 0-80 ℃.
10. The method of claim 1, wherein the method comprises: and the separation method in the step two is one or more of centrifugation, spray drying, suction filtration and freeze drying.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445169A (en) * | 2014-12-03 | 2015-03-25 | 安徽百特新材料科技有限公司 | Method for preparing grapheme by means of aqueous phase cutting and stripping |
| CN105600781A (en) * | 2016-03-02 | 2016-05-25 | 合肥国轩高科动力能源有限公司 | Method for preparing single-layer graphene through CO2 intercalation assisted by ball milling |
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- 2021-08-24 CN CN202110971908.7A patent/CN113683084A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445169A (en) * | 2014-12-03 | 2015-03-25 | 安徽百特新材料科技有限公司 | Method for preparing grapheme by means of aqueous phase cutting and stripping |
| CN105600781A (en) * | 2016-03-02 | 2016-05-25 | 合肥国轩高科动力能源有限公司 | Method for preparing single-layer graphene through CO2 intercalation assisted by ball milling |
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Application publication date: 20211123 |