CN111017916A - Preparation method of graphene with controllable layer number - Google Patents
Preparation method of graphene with controllable layer number Download PDFInfo
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- CN111017916A CN111017916A CN202010011948.2A CN202010011948A CN111017916A CN 111017916 A CN111017916 A CN 111017916A CN 202010011948 A CN202010011948 A CN 202010011948A CN 111017916 A CN111017916 A CN 111017916A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010410 layer Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003791 organic solvent mixture Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000000703 high-speed centrifugation Methods 0.000 claims description 2
- 238000009830 intercalation Methods 0.000 claims description 2
- 230000002687 intercalation Effects 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims 1
- 230000008014 freezing Effects 0.000 claims 1
- 239000002356 single layer Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000000725 suspension Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 238000004506 ultrasonic cleaning Methods 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 238000001237 Raman spectrum Methods 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000000089 atomic force micrograph Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007740 vapor deposition Methods 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
Abstract
The invention relates to a preparation method of graphene with controllable layer number, which is suitable for preparing graphene sheets with controllable layer number in a macroscopic and bright manner. The method comprises the following steps: 1) uniformly dispersing large-size graphite in methyl pyrrolidone (NMP), and adjusting the pH value of the solution to 11; 2) transferring the uniformly dispersed suspension to a conical flask, putting the conical flask into an ultrasonic cleaning instrument, and performing ultrasonic dispersion to obtain multilayer graphene; 3) and further heating the multilayer graphene dispersion liquid by microwave, ultrasonically stripping for a certain time, putting the solution into a centrifuge tube, centrifuging at high speed, cleaning for three times, and freeze-drying to obtain the few-layer and single-layer graphene materials. The method adopts a microwave heating and ultrasonic stripping combined method to prepare the graphene materials with different layers, has the advantages of cheap and easily-obtained raw materials, simple synthesis device and strong operability of the preparation method, and can quickly synthesize a large amount of graphene nano materials with large specific surface area and stable structure.
Description
Technical Field
The invention relates to the technical field of graphene preparation, in particular to a method for preparing a large amount of graphene with controllable layer number, which is suitable for preparing the graphene with controllable layer number on a large scale.
Background
The graphene is a compound sp2The two-dimensional atomic layer formed by hybridized carbon atoms has unique structure and excellent electrical, thermal and mechanical properties, so that the two-dimensional atomic layer can be applied to composite materials, electronic devices and catalystsThe material has wide application prospect in the fields of chemical materials, battery materials, gas sensors, gas storage and the like. Graphene has become the most interesting material in the carbon material family nowadays and has also become the leading edge of the most active research in the fields of material science and condensed state physics.
The unique electrical properties of graphene underlie its application in numerous fields. The performance of graphene is closely related to the number of layers, and graphene with different number of layers shows different performance. Single-layer graphene is semi-metallic, with only two carriers, electrons and holes, and its carrier is a massless dirac fermi. Meanwhile, the electron mobility can reach 2.5 multiplied by 10 at room temperature5cm2V-1s-1. Single layer graphene can withstand even millions of times more current density than copper. And 3-10 layers of graphene have multiple carriers, and the valence band and the conduction band of the graphene are obviously overlapped. Therefore, the large-scale preparation of the high-quality graphene with controllable layer number is a precondition and guarantee for regulating and controlling the physical and chemical properties and developing application exploration.
Up to now, a large number of methods for preparing graphene have been proposed. These methods can be classified into two broad categories, i.e., bottom-up methods and top-down methods, mainly mechanical stripping methods, chemical vapor deposition methods, redox methods, and the like. Although the obtained lamella is complete by the mechanical stripping method, the preparation period is long, the randomness is high, the preparation efficiency is low, the large-scale preparation cannot be realized, and the method cannot be used in industrial production; although the vapor deposition method has simple process, the transfer difficulty is high, the efficiency is low, the controllability is low, and the vapor deposition method cannot be widely used for industrial production; graphene prepared by a redox method has larger defects in structure and composition, and various performances of the graphene are greatly influenced. Liquid phase stripping is one of the most widely applied methods in the current graphene preparation, and is assisted in stripping by ultrasonic treatment in a specific organic solvent to obtain a graphene sheet layer with high quality and high yield, so that the method is an economical and efficient graphene preparation method.
In order to achieve the purpose, the novel method for preparing a large amount of high-quality graphene with controllable layer number, provided by the invention, has the advantages of simple process flow, easiness in operation, high product quality, good controllability, hopeful mass production and the like, and sequentially comprises the following steps:
step 1: selecting a water/organic solvent mixture as a stripping medium, adding sodium hydroxide as an intercalation agent, and adding a proper amount of graphite for uniform dispersion;
step 2: the mixed solution is subjected to interlayer expansion of graphite by a microwave rapid heating method, and further stripped through ultrasonic treatment;
and step 3: and after the reaction is finished, removing the graphite which is not completely peeled off and the large-size thick graphite flakes by using a high-speed centrifugation method, washing with water, and freeze-drying to obtain the graphene with controllable layer number, high quality and high yield.
The water/organic solvent mixture described in step 1 is an 80% solution of methyl pyrrolidone (NMP), and NaOH is added until the pH of the solution system is 11.
The microwave heating power in the step 2 is 200-300W, and the heating time is 10 minutes; and continuing ultrasonic stripping of the mixed solution subjected to microwave treatment for 30-90 minutes at the power of 250W.
In the step 3, the mixed solution is centrifuged at 1500-10000rpm for 20 minutes, then washed with water for three times, frozen to obtain a frozen object, and frozen and dried to obtain a product.
The invention has the beneficial effects that:
the method for preparing a large amount of graphene with controllable layer number provided by the invention adopts a liquid phase stripping method combining ultrasonic and microwave heating, has the advantages of cheap and easily-obtained raw materials, simple synthesis device and strong operability of the preparation method, can quickly synthesize a large amount of graphene nano materials with different layer numbers, large specific surface area and stable structure, and solves the defect of harsh conditions for preparing single-layer graphene at present.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Drawings
FIG. 1: the invention prepares the transmission electron microscope images of graphene with different layers, wherein a is the TEM image of example 1, b is the TEM image of example 2, and c is the TEM image of example 3. As can be seen from the figure, the graphene obtained by the method has a relatively flat surface;
FIG. 2: typical atomic force microscope photos of graphene with different layers and corresponding thicknesses are prepared; wherein a is the AFM map of example 1, b is the AFM map of example 2, and c is the AFM map of example 3.
FIG. 3: raman (Raman) spectra of graphene with different layers are prepared;
Detailed Description
Example 1:
0.5g of artificial graphite powder (2-5 mu m) is weighed, wherein the methyl pyrrolidone with the mass concentration of 80% is added and mixed evenly, and then a proper amount of NaOH aqueous solution is added to adjust the pH value of the solution to 11. The obtained mixed solution was uniformly mixed in a magnetic stirrer for 30min, and then subjected to ultrasonic treatment in an ultrasonic cleaner for 120 min (250W). The resulting suspension was transferred to a centrifuge tube and centrifuged at 1500rpm for 20 minutes. Washing the obtained black precipitate with deionized water for three times, and freeze-drying for 48 hours to obtain powdery multilayer graphene.
As can be seen from the TEM image in fig. 1a, the product obtained in example 1 has a multilayer layered structure, with distinct overlapping edges, but a flat surface, and the AFM image in fig. 2a confirms that the obtained multilayer graphene sheet has a thickness of 6.4nm, which is equivalent to 6-8 layers of graphene. The raman spectrum of fig. 3 shows that the raman spectrum 2D peak of the multilayer graphene sample is asymmetric with two peaks. The yield of the multilayer graphene is close to 100%, and the layer number distribution is uniform.
Example 2:
0.5g of artificial graphite powder (2-5 mu m) is weighed, wherein the methyl pyrrolidone with the mass concentration of 80% is added and mixed evenly, and then a proper amount of NaOH aqueous solution is added to adjust the pH value of the solution to 11. The obtained mixed solution is placed in a magnetic stirrer to be uniformly mixed for 30min, the mixed solution is transferred into a microwave reactor after being subjected to ultrasonic treatment for 120 min, the mixed solution is heated for 10 min (150 ℃) at 300W, and the mixed solution is poured into a centrifuge tube after being cooled and is subjected to ultrasonic treatment for 30min (250W). The resulting suspension was transferred to a centrifuge tube and centrifuged at 3500rpm for 20 minutes. Washing the obtained black precipitate with deionized water for three times, and freeze-drying for 48 hours to obtain powdery multilayer graphene.
From the TEM image of fig. 1b, the product obtained in example 2 is a few-layer layered nanosheet structure and has a flat surface, and the AFM image of fig. 2b confirms that the obtained few-layer graphene sheet has a thickness of 1.7nm, which is equivalent to 2-3 layers of graphene. The raman spectrum of fig. 3 shows that the raman spectrum 2D peak of the few-layer graphene sample is asymmetric with two peaks. The yield of the few-layer graphene is close to 100%, and the layer number distribution is uniform.
Example 3:
the difference from the embodiment 2 is that: after the microwave treatment of the mixture, the sonication was extended to 90 minutes (250W). The resulting suspension was transferred to a centrifuge tube and centrifuged at 10000rpm for 20 minutes. Washing the obtained black supernatant with deionized water for three times, and freeze-drying for 48 hours to obtain powdery multilayer graphene.
As can be seen from the TEM image in fig. 1c, the product obtained in example 3 is a single-layer nanosheet, the surface of the graphene is relatively flat, and a certain degree of wrinkles and curls appear in some places, and the AFM image in fig. 2c confirms that the thickness of the obtained single-layer graphene sheet is 1.1 nm. The raman spectrum of fig. 3 shows that the 2D peak of the raman spectrum of the single-layer graphene sample is more sharp and clearly red-shifted. The yield of the single-layer graphene is close to 70%, and the layer number distribution is uniform.
Claims (8)
1. A preparation method of graphene with controllable layer number is characterized by adopting a liquid phase stripping method and comprising the following steps:
step 1: selecting a water/organic solvent mixture as a stripping medium, adding sodium hydroxide as an intercalation agent, and adding a proper amount of graphite for uniform dispersion;
step 2: the mixed solution is subjected to interlayer expansion of graphite by a microwave rapid heating method, and further stripped through ultrasonic treatment;
and step 3: and after the reaction is finished, removing the graphite which is not completely peeled off and the large-size thick graphite flakes by using a high-speed centrifugation method, washing with water, and freeze-drying to obtain the graphene with controllable layer number.
2. The method for preparing graphene according to claim 1, wherein the number of layers is controlled by: the water/organic solvent mixture described in step 1 is an 80% solution of methyl pyrrolidone (NMP), and NaOH is added until the pH of the solution system is 11.
3. The method for preparing graphene according to claim 1, wherein the number of layers is controlled by: the microwave heating power in the step 2 is 200-300W, and the heating time is 10 minutes; and continuing ultrasonic stripping of the mixed solution subjected to microwave treatment for 30-90 minutes at the power of 250W.
4. The method for preparing graphene according to claim 1, wherein the number of layers is controlled by: in the step 3, the mixed solution is centrifuged at 1500-10000rpm for 20 minutes, then washed with water for three times, frozen to obtain a frozen object, and frozen and dried to obtain a product.
5. The method for preparing graphene according to claim 1 or 3, wherein the number of layers is controllable: the microwave heating power in the step 2 is 300W, and the heating time is 10 minutes; the ultrasonic stripping of the mixed solution after the microwave treatment is continued for 30 minutes at the power of 250W.
6. The method for preparing graphene according to claim 1 or 3, wherein the number of layers is controllable: the microwave heating power in the step 2 is 200W, and the heating time is 10 minutes; the ultrasonic stripping of the mixed solution after the microwave treatment is continued for 90 minutes at the power of 250W.
7. The method for preparing graphene according to claim 1 or 4, wherein the number of layers is controllable: in step 3, the mixed solution is centrifuged at 3500rpm for 20 minutes, then washed with water three times, frozen to obtain a frozen substance, and then frozen and dried to obtain the product.
8. The method for preparing graphene according to claim 1 or 4, wherein the number of layers is controllable: and 3, centrifuging the mixed solution at 10000rpm for 20 minutes, washing with water for three times, freezing to obtain a frozen object, and freeze-drying to obtain a product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079351A (en) * | 2020-09-01 | 2020-12-15 | 深圳市超导新材料有限公司 | Preparation method of nitrogen-containing few-layer graphene |
| CN112390248A (en) * | 2020-11-20 | 2021-02-23 | 金陵科技学院 | Preparation and testing method of modified graphene conductive material |
| CN114014307A (en) * | 2021-12-07 | 2022-02-08 | 湖南润众新材料科技有限公司 | Preparation method of few-layer cryptocrystalline graphene |
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Application publication date: 20200417 |