CN114477154A - Preparation method of high-quality graphene - Google Patents
Preparation method of high-quality graphene Download PDFInfo
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- CN114477154A CN114477154A CN202210276387.8A CN202210276387A CN114477154A CN 114477154 A CN114477154 A CN 114477154A CN 202210276387 A CN202210276387 A CN 202210276387A CN 114477154 A CN114477154 A CN 114477154A
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- C01—INORGANIC CHEMISTRY
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- 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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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
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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
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
Abstract
The invention relates to the technical field of graphene preparation, and particularly discloses a preparation method of high-quality graphene. The preparation method of the high-quality graphene comprises the following steps: mixing graphite powder with a stripping agent, an auxiliary stripping agent and an intercalating agent, reacting for 1-12 h, then quenching with water, and washing and drying a reaction product to obtain the high-quality graphene. The method disclosed by the invention is safe and environment-friendly, is simple and convenient to operate, has low production cost, and can be used for efficiently preparing high-quality graphene with few layers and few defects.
Description
Technical Field
The invention relates to the technical field of graphene preparation, in particular to a preparation method of high-quality graphene.
Background
In 2004, the university of manchester, uk, k.s.novoseov and a.k.geim used a mechanical stripping process to produce single-layer graphene and won't be prize in 2010. The graphene is represented by sp2The hybridized carbon atoms are connected with 3 adjacent carbon atoms through sigma bonds to form a regular hexagonal honeycomb-shaped planar structure, and the residual p orbitals on each carbon atom and the adjacent carbon atoms are mutually overlapped to form pi bonds, so that the graphene has excellent electrical properties. The graphene has larger theoretical specific surface area (2630 m)2g-1) High carrier mobility (2 × 10)5cm2v-1s-1) High Young's modulus (1.0 TPa), high thermal conductivity (5000 Wm)-1 K-1) High light transmittance (97.7%) and high conductivity (> 6X 10)6S/m). The two-dimensional graphene has excellent optical, electrical, thermal and mechanical properties and the like, has huge application prospects in a plurality of traditional industries and strategic emerging industries, and is known as a next generation key base material. However, a bottleneck problem in the industrialization and application of graphene is how to prepare high-quality graphene products with high efficiency, large scale, low cost and environmental friendliness.
The preparation method of the graphene mainly comprises a mechanical stripping method, a chemical vapor deposition method, a SiC epitaxial growth method, a redox method and a liquid phase stripping method. The chemical vapor deposition method can synthesize high-quality graphene, but is not easy to operate, the size, the number of layers and the shape of the graphene are not easy to control, the preparation cost is high, the yield is low, and the problems seriously limit the large-scale production of the graphene. The SiC epitaxial growth method can produce high-quality graphene, but when the graphene is produced by the method, conditions such as temperature, pressure, substrate and the like need to be accurately controlled, and production equipment is expensive, which is not favorable for large-scale industrial production. Graphene can be prepared in a large scale by a redox method, and GO contains a large number of oxygen-containing functional groups such as hydroxyl, carboxyl and the like, so that GO can be stably dispersed in water, which is very beneficial to wide application of GO. However, many harmful gases and a large amount of corrosive waste liquid are generated in the process of GO preparation and reduction, which easily causes environmental pollution, and the rGO has a large amount of structural defects, which severely limits the wide application of the rGO, especially in the aspects of lithium ion batteries, sodium ion batteries, lithium sulfur batteries and the like. The mechanical exfoliation method can produce high-quality graphene, and the method is widely applied to basic research. However, the method is complex to operate, high in equipment requirement, low in production efficiency and yield of graphene, and not suitable for large-scale production of graphene. The graphene prepared by the liquid phase stripping method has fewer structural defects and lower oxygen content, and the method is simple and convenient to operate, simple in post-treatment and various in production modes. However, liquid phase exfoliation methods are often affected by poor exfoliation efficiency and low graphene concentrations (typically < 0.1 mg/mL).
The Chinese patent application No. CN201610642713.7 discloses a method for preparing graphene powder at room temperature, wherein in the preparation method, graphite is prepared into a graphene precursor in the first step, and the graphene precursor is placed in a solution to be ultrasonically stripped to prepare a graphene dispersion liquid in the second step. In addition, the method is difficult to control the number of layers and defects of the prepared graphene; it is difficult to obtain graphene with few layers and few defects (D peak/G peak of 0.3 or less); high-quality graphene cannot be prepared.
Disclosure of Invention
In order to overcome at least one technical problem in the prior art, the invention provides a preparation method of high-quality graphene.
The technical problem to be solved by the invention is realized by the following technical scheme:
a preparation method of high-quality graphene comprises the following steps: mixing graphite powder with a stripping agent, an auxiliary stripping agent and an intercalating agent, reacting for 1-12 h, then quenching with water, and washing and drying a reaction product to obtain the high-quality graphene.
According to the method, the stripping agent, the auxiliary stripping agent and the intercalation agent are added into the graphite powder to prepare the graphene; meanwhile, the addition of the stripping agent, the auxiliary stripping agent and the intercalation agent can complete the reaction in one step, greatly simplify the reaction steps, and simultaneously can prepare the graphene with few layers and few defects.
Here, the inventors need to emphasize that the graphite powder must be added with an exfoliant, an auxiliary exfoliant and an intercalator at the same time to prepare graphene; if the auxiliary stripping agent or the intercalation agent is not added, the graphene cannot be prepared in one step, and the graphene with few layers and few defects cannot be prepared.
Preferably, the stripping agent is nitric acid.
Preferably, the nitric acid is 60-70% by mass.
Most preferably, the nitric acid is 68% by weight.
Preferably, the auxiliary stripping agent is selected from K2SO4、Na2SO4、(NH4)2SO4、CuSO4、ZnSO4、A12(SO4)3、Fe2(SO4)3One or a mixture of two or more of them.
Preferably, the intercalating agent is selected from metal peroxides.
Most preferably, the metal peroxide is one or a mixture of more than two of sodium peroxide, potassium peroxide, calcium peroxide, magnesium peroxide, zinc peroxide and strontium peroxide.
The inventor surprisingly finds out in the research that, in the method of the invention, the selection of the intercalation agent plays a crucial role in preparing the graphene with few layers and few defects; the inventors have unexpectedly found in a large number of experimental procedures: in the method, when the intercalation agent selects the metal peroxide, the intercalation agent can prepare the graphene with excellent performance, few layers and few defects, wherein the content of the graphene with less than 5 layers reaches more than 85 percent, the content of the graphene with 1 layer reaches more than 50 percent, and ID/IGThe value is less than 0.15. However, the intercalation agent selects other peroxides (such as peroxy acid salt) or other substances as the intercalation agent, and the performance of the prepared graphene is far inferior to that of the graphene in the aspects of few layers, few defects and the like.
Preferably, the dosage ratio of the graphite powder to the stripping agent, the auxiliary stripping agent and the intercalating agent is 0.1-0.3 g: 10-20 mL: 2-3.5 g: 3-6.5 g.
Most preferably, the ratio of the graphite powder to the stripping agent, the auxiliary stripping agent and the intercalating agent is 0.1 g: 10 mL: 2 g: 5 g.
Preferably, the reaction is: stirring and/or ultrasonic reaction is carried out for 1-12 h at the temperature of 35-70 ℃.
Most preferably, the reaction is: stirring and/or ultrasonic reaction is carried out for 2.5-7 h at the temperature of 35-70 ℃.
Preferably, the washing is carried out with water.
Has the advantages that: the invention provides a brand-new preparation method of graphene, which enables graphite to be efficiently stripped into high-quality graphene under the combined action of a stripping agent, an auxiliary stripping agent and an intercalating agent; in addition, the method is safe and environment-friendly, is simple and convenient to operate, is low in cost, and can be used for efficiently preparing the product with few layers and few defects (I)D/IG0.3 or less) of high quality graphene.
Detailed Description
The present invention is further explained below with reference to specific examples, which are not intended to limit the present invention in any way.
Example 1
2g of Na is added into a reaction kettle2SO4Adding 10mL of concentrated nitric acid with the mass fraction of 68%, stirring for 6h at 35 ℃, quenching the reaction with water, filtering the mixture to obtain a precipitate, washing the precipitate with a large amount of water, and finally drying the precipitate in a vacuum drying oven at 60 ℃ for one night to obtain the high-quality graphene.
Example 2
2.5gK is added into the reaction kettle2SO4Adding 15mL of concentrated nitric acid with the mass fraction of 68%, stirring for 3 hours at 50 ℃, quenching the reaction with water, filtering the mixture to obtain a precipitate, washing the precipitate with a large amount of water, and finally drying the precipitate in a vacuum drying oven at 60 ℃ for one night to obtain the high-quality graphene.
Example 3
2.3g of CuSO is added into a reaction kettle4The preparation method comprises the following steps of adding 17mL of concentrated nitric acid with the mass fraction of 68% into 6.2g of calcium peroxide and 0.25g of graphite powder, stirring for 2.5 hours at 65 ℃, quenching the reaction with water, filtering the mixture to obtain a precipitate, washing the precipitate with a large amount of water, and freeze-drying the precipitate in a freeze dryer for one night to obtain the high-quality graphene.
Example 4
3.1g (NH) was added to the reactor4)2SO42.6g of magnesium peroxide and 0.15g of graphite powder, then adding 12mL of concentrated nitric acid with the mass fraction of 68%, stirring for 7 hours at 45 ℃, quenching the reaction with water, filtering the mixture to obtain a precipitate, washing the precipitate with a large amount of water, and finally drying the precipitate in a vacuum drying oven at 60 ℃ for one night to obtain the high-quality graphene.
Example 5
2.6g of ZnSO is added into a reaction kettle43.1g of zinc peroxide and 0.2g of graphite powder, and then 18mL of the mixture is added68% concentrated nitric acid, stirring at 70 ℃ for 7 hours, quenching the reaction with water, filtering the mixture to obtain a precipitate, washing the precipitate with a large amount of water, and finally drying the precipitate in a vacuum drying oven at 80 ℃ for one night to obtain the product, namely the high-quality graphene.
Comparative example 1
2g of Na is added into a reaction kettle2SO45g of sodium percarbonate and 0.1g of graphite powder, then 10mL of concentrated nitric acid with the mass fraction of 68% is added, then the mixture is stirred for 6 hours at the temperature of 35 ℃, the reaction is quenched by water, the mixture is filtered to obtain a precipitate, a large amount of water is used for washing the precipitate, and finally the precipitate is placed in a vacuum drying oven at the temperature of 60 ℃ to be dried for one night to obtain a product, namely graphene.
Comparative example 1 differs from example 1 in that comparative example 1 employs a peroxyacid salt (sodium percarbonate) as the intercalating agent, whereas example 1 employs a metal peroxide (sodium peroxide) as the intercalating agent.
Comparative example 2
2g of Na is added into a reaction kettle2SO45g of potassium monopersulfate and 0.1g of graphite powder, then 10mL of concentrated nitric acid with the mass fraction of 68% is added, then the mixture is stirred for 6 hours at 35 ℃, the reaction is quenched by water, the mixture is filtered to obtain a precipitate, a large amount of water is used for washing the precipitate, and finally the precipitate is placed in a vacuum drying oven at 60 ℃ and dried for one night to obtain the product, namely graphene.
Comparative example 2 differs from example 1 in that comparative example 2 uses a peroxyacid salt (potassium hydrogen peroxymonosulfate) as the intercalating agent, whereas example 1 uses a metal peroxide (sodium peroxide) as the intercalating agent.
Comparative example 3
2g of Na is added into a reaction kettle2SO45g of calcium ammonium nitrate and 0.1g of graphite powder, then adding 10mL of concentrated nitric acid with the mass fraction of 68%, then stirring for 6 hours at 35 ℃, quenching the reaction with water, filtering the mixture to obtain a precipitate, washing the precipitate with a large amount of water, and finally drying the precipitate in a vacuum drying oven at 60 ℃ for one night to obtain the product, namely graphene.
Comparative example 3 differs from example 1 in that in comparative example 3 calcium ammonium nitrate is used as the intercalating agent, whereas example 1 uses a metal peroxide (sodium peroxide) as the intercalating agent.
Comparative example 4
2g of Na is added into a reaction kettle2SO4And 0.1g of graphite powder, then adding 10mL of concentrated nitric acid with the mass fraction of 68%, stirring for 6h at 35 ℃, quenching the reaction with water, filtering the mixture to obtain a precipitate, washing the precipitate with a large amount of water, and finally drying the precipitate in a vacuum drying oven at 60 ℃ for one night to obtain the product, namely graphene.
Comparative example 4 differs from example 1 in that comparative example 4 does not contain an intercalating agent, whereas example 1 does contain a metal peroxide (sodium peroxide) as an intercalating agent.
Comparative example 5
Adding 5g of sodium peroxide and 0.1g of graphite powder into a reaction kettle, then adding 10mL of concentrated nitric acid with the mass fraction of 68%, stirring for 6 hours at 35 ℃, quenching the reaction with water, filtering the mixture to obtain a precipitate, washing the precipitate with a large amount of water, and finally drying the precipitate in a vacuum drying oven at 60 ℃ for one night to obtain a product, namely graphene.
Comparative example 5 differs from example 1 in that comparative example 5 does not include an auxiliary stripping agent, while example 1 does include an auxiliary stripping agent Na2SO4。
Ratios and I of less than 5 layers and 1 layer of graphene in the graphene prepared in examples 1 to 5 and comparative examples 1 to 5D/IGThe results of the value tests are shown in Table 1.
TABLE 1
| Less than 5 layers | 1 layer of | ID/IGValue of | |
| Example 1 preparation of high quality graphene | 91％ | 62％ | 0.103 |
| Example 2 preparation of high quality graphene | 85％ | 51％ | 0.144 |
| Example 3 preparation of high quality graphene | 88％ | 56％ | 0.121 |
| Example 4 preparation of high quality graphene | 86％ | 53％ | 0.132 |
| Example 5 preparation of high quality graphene | 90％ | 59％ | 0.117 |
| Graphene prepared in comparative example 1 | 47％ | 21％ | 0.428 |
| Comparative example 2 graphene prepared | 50％ | 27％ | 0.410 |
| Comparative example 3 graphene prepared | 42％ | 19％ | 0.476 |
| Comparative example 4 graphene prepared | 35％ | 11％ | 0.598 |
| Graphene prepared in comparative example 5 | 44％ | 20％ | 0.504 |
As can be seen from the experimental data in table 1, in examples 1 to 5, the exfoliation agent, the auxiliary exfoliation agent, and the intercalation agent are simultaneously added to the graphite powder to prepare the graphene with few layers and few defects, wherein the content of the graphene less than 5 layers is more than 85%, the content of the graphene in 1 layer is more than 50%, and I isD/IGA value of less than 0.15; has excellent performance. Among them, the high quality graphene prepared in example 1 has the best performance.
From the experimental data in table 1, it can be seen that the content of the graphene in the comparative examples 1 to 3 is less than that of the graphene in 5 layers and the content of the graphene in 1 layer is far less than that of the high-quality graphene prepared in example 1, and simultaneously, the content of graphene in I layer is far less than that of the high-quality graphene prepared in example 1D/IGThe value is also much higher than that of the high-quality graphene prepared in example 1; this indicates that: plug-inThe selection of the layering agent plays a crucial role in preparing few-layer and few-defect graphene; in the method, the metal peroxide is used as the intercalating agent, so that the content of less than 5 layers of graphene and 1 layer of graphene can be greatly increased compared with the case that other substances are used as the intercalating agent, and the I content of the prepared graphene can be greatly reducedD/IGThe value is obtained.
It can be seen from the experimental data in table 1 that the content of the graphene prepared in comparative examples 4 and 5 is less than that of the graphene prepared in 5 layers and the content of the graphene prepared in 1 layer is much less than that of the high-quality graphene prepared in example 1, and I is the same as that of the high-quality graphene prepared in example 1D/IGThe value is also much higher than that of the high-quality graphene prepared in example 1; this indicates that: the method comprises the following steps of (1) preparing graphene by adding a stripping agent, an auxiliary stripping agent and an intercalating agent into graphite powder at the same time; the prepared graphene has a high content of less than 5 layers and 1 layer of graphene; and can ensure that the prepared graphene has lower ID/IGThe value is obtained. Without adding an auxiliary stripping agent or an intercalation agent, the graphene with higher content less than 5 layers and 1 layer can not be prepared in one step, and the prepared graphene with lower I can not be ensuredD/IGThe value is obtained.
Claims (10)
1. A preparation method of high-quality graphene is characterized by comprising the following steps: mixing graphite powder with a stripping agent, an auxiliary stripping agent and an intercalating agent, reacting for 1-12 h, then quenching with water, and washing and drying a reaction product to obtain the high-quality graphene.
2. The method of claim 1, wherein the stripping agent is nitric acid.
3. The preparation method of high-quality graphene according to claim 1, wherein nitric acid with a mass fraction of 60-70% is selected as the nitric acid;
most preferably, the nitric acid is 68% by weight.
4. The method for preparing high-quality graphene according to claim 1, wherein the auxiliary release agent is selected from K2SO4、Na2SO4、(NH4)2SO4、CuSO4、ZnSO4、Al2(SO4)3、Fe2(SO4)3One or a mixture of two or more of them.
5. The method for preparing high-quality graphene according to claim 1, wherein the intercalation agent is selected from metal peroxides.
6. The method for producing high-quality graphene according to claim 1, wherein the metal peroxide is one or a mixture of two or more selected from the group consisting of sodium peroxide, potassium peroxide, calcium peroxide, magnesium peroxide, zinc peroxide, and strontium peroxide.
7. The preparation method of high-quality graphene according to claim 1, wherein the dosage ratio of the graphite powder to the stripping agent, the auxiliary stripping agent and the intercalating agent is 0.1-0.3 g: 10-20 mL: 2-3.5 g: 3-6.5 g.
8. The method for preparing high-quality graphene according to claim 7, wherein the dosage ratio of the graphite powder to the exfoliant, the auxiliary exfoliant and the intercalating agent is 0.1 g: 10 mL: 2 g: 5 g.
9. The method for preparing high-quality graphene according to claim 1, wherein the reaction is: stirring and/or ultrasonic reaction are carried out at the temperature of 35-70 ℃.
Most preferably, the reaction is: stirring and/or ultrasonic reaction is carried out for 2.5-7 h at the temperature of 35-70 ℃.
10. The method for preparing high-quality graphene according to claim 1, wherein the washing is carried out with water.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115285987A (en) * | 2022-08-25 | 2022-11-04 | 深圳材启新材料有限公司 | Preparation method of expanded graphite |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452649A (en) * | 2010-10-18 | 2012-05-16 | 中国科学院宁波材料技术与工程研究所 | Preparation method for graphene |
| US20150218002A1 (en) * | 2014-02-05 | 2015-08-06 | Belenos Clean Power Holding Ag | Method of production of graphite oxide and uses thereof |
| CN105836734A (en) * | 2016-03-16 | 2016-08-10 | 中国科学院山西煤炭化学研究所 | Rapid preparation method for high-quality graphene |
| CN106865539A (en) * | 2017-03-01 | 2017-06-20 | 上海昂星科技发展有限公司 | A kind of lipophilic graphene nanometer sheet and its preparation method and application |
| CN107200319A (en) * | 2017-07-19 | 2017-09-26 | 西安交通大学 | One kettle way liquid phase peels off the method for being prepared on a large scale high-quality graphene |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452649A (en) * | 2010-10-18 | 2012-05-16 | 中国科学院宁波材料技术与工程研究所 | Preparation method for graphene |
| US20150218002A1 (en) * | 2014-02-05 | 2015-08-06 | Belenos Clean Power Holding Ag | Method of production of graphite oxide and uses thereof |
| CN105836734A (en) * | 2016-03-16 | 2016-08-10 | 中国科学院山西煤炭化学研究所 | Rapid preparation method for high-quality graphene |
| CN106865539A (en) * | 2017-03-01 | 2017-06-20 | 上海昂星科技发展有限公司 | A kind of lipophilic graphene nanometer sheet and its preparation method and application |
| CN107200319A (en) * | 2017-07-19 | 2017-09-26 | 西安交通大学 | One kettle way liquid phase peels off the method for being prepared on a large scale high-quality graphene |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115285987A (en) * | 2022-08-25 | 2022-11-04 | 深圳材启新材料有限公司 | Preparation method of expanded graphite |
| CN115285987B (en) * | 2022-08-25 | 2023-09-19 | 深圳材启新材料有限公司 | Preparation method of expanded graphite |
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