CN113173580A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN113173580A CN113173580A CN202110547209.XA CN202110547209A CN113173580A CN 113173580 A CN113173580 A CN 113173580A CN 202110547209 A CN202110547209 A CN 202110547209A CN 113173580 A CN113173580 A CN 113173580A
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- graphene
- ball milling
- sulfuric acid
- graphite
- mixed solution
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 30
- 239000010439 graphite Substances 0.000 claims abstract description 30
- 238000000498 ball milling Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003830 anthracite Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000009830 intercalation Methods 0.000 abstract description 2
- 230000002687 intercalation Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- 238000011031 large-scale manufacturing process Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明提供了一种石墨烯的制备方法，包括以下步骤：将石墨和浓硫酸混合得到混合溶液，对所述混合溶液在在Ar气保护下进行高能球磨，高能球磨过程中球磨机转速为1200转/分钟‑1300转/分钟，球磨时间为30‑48小时；球磨完成后经分离、水洗、过滤、干燥得到石墨烯。本发明的方法剥离效果好，得到的石墨烯尺寸小，且作为插层剂的硫酸可反复回用，环境友好，节约资源，工业化应用前景非常广阔。The invention provides a method for preparing graphene, comprising the following steps: mixing graphite and concentrated sulfuric acid to obtain a mixed solution, performing high-energy ball milling on the mixed solution under the protection of Ar gas, and during the high-energy ball milling process, the ball mill rotates at 1200 rpm /min-1300 rev/min, the ball milling time is 30-48 hours; after the ball milling is completed, graphene is obtained through separation, washing, filtration and drying. The method of the invention has good peeling effect, the obtained graphene is small in size, and the sulfuric acid used as the intercalation agent can be reused repeatedly, which is environmentally friendly, saves resources, and has very broad prospects for industrial application.
Description
Technical Field
The invention relates to the field of new materials, in particular to the technical field of graphene, and more particularly relates to a method for industrially preparing graphene.
Background
Graphene is a novel planar two-dimensional carbon material, has unique structural characteristics and excellent mechanical, electrical, optical and thermal properties, and has wide application prospects in the fields of nano-electronic devices, energy storage materials, catalysis, sensors, drug carriers, functional composite materials and the like. In addition, the graphene has great application prospects in the fields of bioengineering and medicine, including targeted drug delivery, cell imaging, biological detection, tumor treatment and the like. However, the existing preparation technology and cost of graphene limit the application and development of graphene.
Due to the excellent physical and chemical properties of graphene, the graphene has great application prospects and requirements in the fields of energy, chemical engineering, materials, biotechnology, aerospace, electric vehicles and the like, so that the development of a novel graphene preparation method which is low in cost, high in yield, free of pollution and capable of realizing large-scale production is an urgent need for graphene industrialization.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a preparation method of graphene. The method has the advantages of low cost, good separation effect, environmental friendliness and large-scale production, and the prepared graphene has a large size, so the method has a very good application prospect.
The invention adopts the following technical scheme:
a method for industrially preparing graphene comprises the following steps:
mixing graphite and concentrated sulfuric acid to obtain a mixed solution, and carrying out high-energy ball milling on the mixed solution under the protection of Ar gas, wherein the rotating speed of a ball mill is 1200-1300 rpm in the high-energy ball milling process, and the ball milling time is 30-48 hours;
and after the ball milling is finished, separating, washing, filtering and drying to obtain the graphene.
The weight-volume ratio of the mass of the graphite to the concentrated sulfuric acid is 1: 50-1: 500 g/mL.
The mass concentration of the concentrated sulfuric acid is 75-98%.
The graphite is selected from crystalline flake graphite, expandable graphite or a product of anthracite sintered at the temperature of 1200-1300 ℃.
The mixed solution is also added with hydrogen peroxide with the mass concentration of 30-45%. The addition of the hydrogen peroxide can accelerate the ball milling process of the graphene, shorten the ball milling time to 10-15 hours and quickly obtain the high-quality graphene.
The separated graphene and sulfuric acid can be recycled, resources are saved, and graphite flakes are basically and completely stripped to form graphene.
The particle size of the large-size graphene prepared by the method is less than 5 mu m, and the graphene prepared by stripping by the method can also realize large-scale production. In the invention, high-concentration sulfuric acid and graphite are weighed according to a certain proportion and are mixed and then ball-milled. Sulfuric acid is used as an necessary intercalation agent for graphite stripping, and natural graphite flakes are effectively stripped through long-time sulfuric acid bath high-energy ball milling. The stripped graphene can float on the upper layer of a sulfuric acid solution due to the fact that the specific gravity becomes light, the graphene floating on the upper layer is collected, distilled water is added for washing, the incompletely separated graphene can be still located below the stripped graphene due to the fact that the specific gravity is heavy. High-quality graphene can float on the water surface, and the upper graphene layer finally obtained is the graphene with excellent quality through washing and separation. The residual graphite which is not completely separated can be recycled and subjected to ultrasonic separation again, a large amount of acid is not discharged basically in the whole process, and waste acid caused by introducing an oxidant is not generated, so that the method for preparing the large-size graphene with high efficiency, environmental protection, large scale and no pollution is realized.
The invention has the beneficial effects that:
the invention provides a method for industrially preparing graphene, wherein graphite and concentrated sulfuric acid are mixed according to a certain proportion and then are subjected to ball milling treatment to obtain graphene with excellent quality floating on an upper layer, and graphite which is not completely stripped sinks on a lower layer of a solution and can be recycled for further ball milling. The method has the advantages of repeated recycling of sulfuric acid, resource saving, avoidance of waste acid discharge and environmental friendliness. The method solves the problems of high cost, low efficiency, environmental pollution and incapability of industrial large-scale production in the existing graphene preparation technology. In addition, the invention provides a novel method for industrially preparing graphene.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
The preparation method of the graphene comprises the following steps:
(1) weighing 10g of flake graphite and 1L of concentrated sulfuric acid with the mass concentration of 80%, and mixing to form a mixed solution, wherein the volume ratio of the mass of the graphite flake to the concentrated sulfuric acid is 1:100 g/mL;
(2) putting the mixed solution of the graphite and the concentrated sulfuric acid into a high-energy ball mill, and performing ball milling for 38 hours at the rotating speed of 1200 revolutions per minute; after the ball milling is finished, graphene is obtained through separation, washing, filtering and drying, 7.6g of graphene is obtained, and the particle size of the graphene is smaller than 4 microns. The separated sulfuric acid is recycled after being collected.
Example 2
The preparation method of the graphene comprises the following steps:
(1) weighing 10g of anthracite sintered product at 1200 ℃ and 1L of concentrated sulfuric acid with the mass concentration of 98%, and mixing to form a mixed solution, wherein the volume ratio of the mass of the graphite flake to the concentrated sulfuric acid is 1:100 g/mL;
(2) putting the mixed solution of the graphite and the concentrated sulfuric acid into a high-energy ball mill, and performing ball milling for 38 hours at the rotating speed of 1200 revolutions per minute; and after the ball milling is finished, separating, washing, filtering and drying to obtain 8.2g of graphene, wherein the particle size of the graphene is less than 3 microns. The separated sulfuric acid is recycled after being collected.
Example 3
The preparation method of the graphene comprises the following steps:
(1) weighing 10g of anthracite sintered product at 1200 ℃ and 1L of concentrated sulfuric acid with the mass concentration of 70%, and mixing to form a mixed solution, wherein the volume ratio of the mass of the graphite flake to the concentrated sulfuric acid is 1:100 g/mL;
(2) putting the mixed solution of the graphite and the concentrated sulfuric acid into a high-energy ball mill, and performing ball milling for 38 hours at the rotating speed of 1200 revolutions per minute; after ball milling is finished, graphene is obtained through separation, washing, filtering and drying, 5.5g of graphene is obtained, and the particle size of the graphene is smaller than 8 microns. The separated sulfuric acid is recycled after being collected.
Example 4
The preparation method of the graphene comprises the following steps:
(1) weighing 10g of flake graphite and 1L of concentrated sulfuric acid with the mass concentration of 85%, and mixing to form a mixed solution, wherein the volume ratio of the mass of the graphite flake to the volume of the concentrated sulfuric acid is 1:100 g/mL;
(2) putting the mixed solution of the graphite and the concentrated sulfuric acid into a high-energy ball mill, and performing ball milling for 45 hours at the rotating speed of 1300 revolutions per minute; and after the ball milling is finished, separating, washing, filtering and drying to obtain 8.8g of graphene, wherein the particle size of the graphene is less than 8 microns. The separated sulfuric acid is recycled after being collected.
Example 5
The preparation method of the graphene comprises the following steps:
(1) weighing 10g of flake graphite and 1L of concentrated sulfuric acid with the mass concentration of 85%, and mixing to form a mixed solution, wherein the volume ratio of the mass of the graphite flake to the volume of the concentrated sulfuric acid is 1:100 g/mL;
(2) putting the mixed solution of the graphite and the concentrated sulfuric acid into a high-energy ball mill, adding 35% hydrogen peroxide by mass concentration, and performing ball milling for 10 hours at the rotating speed of 1300 r/min; and after the ball milling is finished, separating, washing, filtering and drying to obtain 9.3g of graphene, wherein the particle size of the graphene is less than 3 microns. The separated sulfuric acid is recycled after being collected.
Claims (5)
1. A preparation method of graphene is characterized by comprising the following steps:
mixing graphite and concentrated sulfuric acid to obtain a mixed solution, and carrying out high-energy ball milling on the mixed solution under the protection of Ar gas, wherein the rotating speed of a ball mill is 1200-1300 rpm in the high-energy ball milling process, and the ball milling time is 30-48 hours;
and after the ball milling is finished, separating, washing, filtering and drying to obtain the graphene.
2. The preparation method of graphene according to claim 1, wherein the weight-to-volume ratio of the mass of graphite to concentrated sulfuric acid is 1:50 to 1:500 g/mL.
3. The graphene preparation method according to claim 1, wherein the mass concentration of the concentrated sulfuric acid is 75-98%.
4. The method for preparing graphene according to claim 1, wherein the graphite is selected from crystalline flake graphite, expandable graphite, or a product of anthracite sintered at 1200-1300 ℃.
5. The method according to claim 1, wherein hydrogen peroxide is further added to the mixed solution at a mass concentration of 30 to 45%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110547209.XA CN113173580A (en) | 2021-05-19 | 2021-05-19 | Preparation method of graphene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110547209.XA CN113173580A (en) | 2021-05-19 | 2021-05-19 | Preparation method of graphene |
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| CN113173580A true CN113173580A (en) | 2021-07-27 |
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| CN202110547209.XA Pending CN113173580A (en) | 2021-05-19 | 2021-05-19 | Preparation method of graphene |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163417A (en) * | 2013-05-20 | 2014-11-26 | 东丽先端材料研究开发（中国）有限公司 | Method for preparing graphene by peeling off graphite |
| CN105883767A (en) * | 2014-12-09 | 2016-08-24 | 戴加龙 | Batch preparation method of graphene |
| CN106554010A (en) * | 2015-09-25 | 2017-04-05 | 苏州烯时代石墨烯科技有限公司 | The method of preparation of industrialization big size graphene |
| CN106800293A (en) * | 2017-02-21 | 2017-06-06 | 中国科学院理化技术研究所 | Partially hydroxylated graphene and preparation method thereof |
-
2021
- 2021-05-19 CN CN202110547209.XA patent/CN113173580A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163417A (en) * | 2013-05-20 | 2014-11-26 | 东丽先端材料研究开发（中国）有限公司 | Method for preparing graphene by peeling off graphite |
| CN105883767A (en) * | 2014-12-09 | 2016-08-24 | 戴加龙 | Batch preparation method of graphene |
| CN106554010A (en) * | 2015-09-25 | 2017-04-05 | 苏州烯时代石墨烯科技有限公司 | The method of preparation of industrialization big size graphene |
| CN106800293A (en) * | 2017-02-21 | 2017-06-06 | 中国科学院理化技术研究所 | Partially hydroxylated graphene and preparation method thereof |
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Application publication date: 20210727 |
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