CN113247889A - Method for preparing double-layer graphene - Google Patents
Method for preparing double-layer graphene Download PDFInfo
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- CN113247889A CN113247889A CN202110667704.4A CN202110667704A CN113247889A CN 113247889 A CN113247889 A CN 113247889A CN 202110667704 A CN202110667704 A CN 202110667704A CN 113247889 A CN113247889 A CN 113247889A
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- Prior art keywords
- intercalation compound
- layer graphene
- graphite intercalation
- graphite
- double
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 32
- 239000010439 graphite Substances 0.000 claims abstract description 32
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 238000009830 intercalation Methods 0.000 claims abstract description 19
- 230000002687 intercalation Effects 0.000 claims abstract description 19
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940117975 chromium trioxide Drugs 0.000 claims abstract description 11
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
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
-
- 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 discloses a method for preparing double-layer graphene, which comprises the following specific steps: firstly, graphite, chromium trioxide and concentrated hydrochloric acid with the molar concentration of 12mol/L are reacted at room temperature to prepare a second-order graphite intercalation compound, then the second-order graphite intercalation compound is reacted with oxalic acid at 60 ℃, carbon dioxide generated in the reaction process and generated heat expand the second-order graphite intercalation compound, and finally the exfoliated graphite is double-layer graphene. The invention has the following beneficial effects: 1. the material is cheap and easy to obtain, the equipment is simple, and the manufacturing cost is low; 2. the reaction condition is 60 ℃, normal pressure, mild and does not need high temperature and high pressure; 3. the solvent used in the stripping process is a hydrosolvent, and other organic solvents do not need to be added; 4. the stripping yield is high, the selectivity is more than 63%, and the operation and the post-treatment process of the method are simple.
Description
Technical Field
The invention belongs to the technical field of energy and new material synthesis, and particularly relates to a method for preparing double-layer graphene by using a second-order graphite intercalation compound and oxalic acid under mild conditions.
Background
Graphene is the thinnest novel three-dimensional carbon nanomaterial with the greatest strength and the strongest electric and heat conducting performance found at present. Graphene is called 'black gold', which is the king of new materials, scientists even predict that graphene will 'completely change the 21 st century', and have the possibility of turning over a subversive new technology and a new industrial revolution around the world. Due to its unique properties, graphene has wide applications in the fields of solar cells, sensors, nanoelectronics, high-performance nanoelectronic devices, composite materials, field emission materials, gas sensors, energy storage, and the like. At present, the preparation method of graphene mainly comprises a micro-mechanical stripping method, an epitaxial growth method, a vapor deposition method, an electrochemical stripping method, a solvothermal method, a liquid phase stripping method and the like, wherein the liquid phase stripping method is widely applied due to the characteristics of simple operation and low cost. However, the liquid phase stripping process has some disadvantages in some respects: the prepared graphene product has poor selectivity and low yield; large amounts of toxic solvents are required; the solvents and auxiliary reagents used are expensive and difficult to remove. In view of this, it is an urgent need to solve the problem of developing a method for preparing graphene, which has high selectivity, high yield, uses a green solvent, and is simple to operate.
Disclosure of Invention
The invention solves the technical problem of providing a method for preparing double-layer graphene, which is convenient and efficient, has high selectivity and high yield.
The invention adopts the following technical scheme for solving the technical problems, and the method for preparing the double-layer graphene is characterized by comprising the following specific steps: firstly, graphite, chromium trioxide and concentrated hydrochloric acid with the molar concentration of 12mol/L are reacted at room temperature to prepare a second-order graphite intercalation compound, then the second-order graphite intercalation compound is reacted with oxalic acid at 60 ℃, carbon dioxide generated in the reaction process and generated heat expand the second-order graphite intercalation compound, and finally the exfoliated graphite is double-layer graphene.
More preferably, the feeding ratio of the graphite, the chromium trioxide and HCl in concentrated hydrochloric acid is 0.1g to 0.016 mol.
Further preferably, the feeding ratio of the second-order graphite intercalation compound to oxalic acid is 0.1g to 0.012 mol.
The method for preparing the double-layer graphene is characterized by comprising the following specific steps of: adding 0.1g of graphite and 0.016mol of chromium trioxide into a flask in sequence, adding concentrated hydrochloric acid with the molar concentration of 12mo/L through a constant-pressure dropping funnel, wherein the molar ratio of HCl to chromium trioxide in the concentrated hydrochloric acid is 1:1, stirring and reacting for 2.5h at room temperature, then adding a mixed solution of water and acetone into a reaction mixture, washing, filtering, repeating the above process until the mixed solution is colorless and neutral, drying at 75 ℃ for 2h to obtain a second-order graphite intercalation compound, reacting 0.1g of the second-order graphite intercalation compound and 0.012mol of oxalic acid in an acid system at 60 ℃ for 72h, centrifuging at high speed to remove a supernatant, adding secondary distilled water, carrying out ultrasonic washing for three times, taking out a precipitate, and carrying out vacuum drying at 30 ℃ for 12h to obtain the double-layer graphene.
The invention utilizes carbon dioxide generated by the reaction of a second-order graphite intercalation compound and oxalic acid and the generated heat to expand graphite to prepare the double-layer graphene. Compared with the prior art, the method has the following advantages: 1. the material is cheap and easy to obtain, the equipment is simple, and the manufacturing cost is low; 2. the reaction condition is 60 ℃, normal pressure, mild and does not need high temperature and high pressure; 3. the solvent used in the stripping process is a hydrosolvent, and other organic solvents do not need to be added; 4. the stripping yield is high, the selectivity is more than 63%, and the operation and the post-treatment process of the method are simple.
Drawings
Fig. 1 is an SEM image of double-layered graphene produced by an embodiment of the present invention;
FIG. 2 is an SEM image of double-layer graphene prepared by an embodiment of the invention;
FIG. 3 is an HR-TEM image of bilayer graphene prepared by an example of the present invention;
FIG. 4 is a SAED diagram of double-layer graphene produced by embodiments of the invention;
fig. 5 is a raman comparison of double-layered graphene prepared according to an example of the present invention with virgin graphite.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Examples
Adding 0.1g of graphite and 0.016mol of chromium trioxide into a flask in sequence, adding concentrated hydrochloric acid with the molar concentration of 12mo/L through a constant-pressure dropping funnel, wherein the molar ratio of HCl to chromium trioxide in the concentrated hydrochloric acid is 1:1, stirring at room temperature for 2.5h, then adding a mixed solution of water and acetone into a reaction mixture, washing, filtering, repeating the above process until the mixed solution is colorless and neutral, drying at 75 ℃ for 2h to obtain a second-order graphite intercalation compound, reacting 0.1g of the second-order graphite intercalation compound and 0.012mol of oxalic acid in an acid system at 60 ℃ for 72h, centrifuging at high speed to remove a supernatant, adding secondary distilled water, carrying out ultrasonic washing for three times, taking out a precipitate, and carrying out vacuum drying at 30 ℃ for 12h to obtain the double-layer graphene.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (4)
1. A method for preparing double-layer graphene is characterized by comprising the following specific steps: firstly, graphite, chromium trioxide and concentrated hydrochloric acid with the molar concentration of 12mol/L are reacted at room temperature to prepare a second-order graphite intercalation compound, then the second-order graphite intercalation compound is reacted with oxalic acid at 60 ℃, carbon dioxide generated in the reaction process and generated heat expand the second-order graphite intercalation compound, and finally the exfoliated graphite is double-layer graphene.
2. The method of claim 1, wherein the graphene is prepared by: the feeding ratio of the graphite, the chromium trioxide and HCl in concentrated hydrochloric acid is 0.1g to 0.016 mol.
3. The method of claim 1, wherein the graphene is prepared by: the feeding proportion of the second-order graphite intercalation compound and oxalic acid is 0.1g to 0.012 mol.
4. The method for preparing double-layer graphene according to claim 1, wherein the method comprises the following specific steps: adding 0.1g of graphite and 0.016mol of chromium trioxide into a flask in sequence, adding concentrated hydrochloric acid with the molar concentration of 12mo/L through a constant-pressure dropping funnel, wherein the molar ratio of HCl to chromium trioxide in the concentrated hydrochloric acid is 1:1, stirring and reacting for 2.5h at room temperature, then adding a mixed solution of water and acetone into a reaction mixture, washing, filtering, repeating the above process until the mixed solution is colorless and neutral, drying at 75 ℃ for 2h to obtain a second-order graphite intercalation compound, reacting 0.1g of the second-order graphite intercalation compound and 0.012mol of oxalic acid in an acid system at 60 ℃ for 72h, centrifuging at high speed to remove a supernatant, adding secondary distilled water, carrying out ultrasonic washing for three times, taking out a precipitate, and carrying out vacuum drying at 30 ℃ for 12h to obtain the double-layer graphene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110667704.4A CN113247889A (en) | 2021-06-16 | 2021-06-16 | Method for preparing double-layer graphene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110667704.4A CN113247889A (en) | 2021-06-16 | 2021-06-16 | Method for preparing double-layer graphene |
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| Publication Number | Publication Date |
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| CN113247889A true CN113247889A (en) | 2021-08-13 |
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| CN202110667704.4A Pending CN113247889A (en) | 2021-06-16 | 2021-06-16 | Method for preparing double-layer graphene |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102431999A (en) * | 2011-09-22 | 2012-05-02 | 中国科学院金属研究所 | Method for preparing high-quality graphene |
| CN104071782A (en) * | 2014-06-27 | 2014-10-01 | 广州市尤特新材料有限公司 | Preparation method of graphene |
| CN107416811A (en) * | 2017-06-21 | 2017-12-01 | 山东欧铂新材料有限公司 | A kind of preparation method of high conductivity graphene |
| US20210113981A1 (en) * | 2019-10-16 | 2021-04-22 | Nanotek Instruments, Inc. | Reactor for continuous production of graphene and 2d inorganic compounds |
-
2021
- 2021-06-16 CN CN202110667704.4A patent/CN113247889A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102431999A (en) * | 2011-09-22 | 2012-05-02 | 中国科学院金属研究所 | Method for preparing high-quality graphene |
| CN104071782A (en) * | 2014-06-27 | 2014-10-01 | 广州市尤特新材料有限公司 | Preparation method of graphene |
| CN107416811A (en) * | 2017-06-21 | 2017-12-01 | 山东欧铂新材料有限公司 | A kind of preparation method of high conductivity graphene |
| US20210113981A1 (en) * | 2019-10-16 | 2021-04-22 | Nanotek Instruments, Inc. | Reactor for continuous production of graphene and 2d inorganic compounds |
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Application publication date: 20210813 |
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