CN113753886A - Expanded graphite and preparation method and application thereof - Google Patents
Expanded graphite and preparation method and application thereof Download PDFInfo
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- CN113753886A CN113753886A CN202110955372.XA CN202110955372A CN113753886A CN 113753886 A CN113753886 A CN 113753886A CN 202110955372 A CN202110955372 A CN 202110955372A CN 113753886 A CN113753886 A CN 113753886A
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- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
Abstract
The invention discloses expanded graphite and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, mixing phosphorus pentoxide, an expanding agent, graphite and sulfuric acid for reaction to prepare a mixture; and S2, mixing the mixture with an expansion aid to react to obtain the expanded graphite. The method provided by the invention can quickly synthesize the chemical expanded graphite, has controllable acid consumption, low energy consumption and simple and safe implementation process, and is suitable for mass production. The method of the invention does not need heating energy consumption, can quickly react at room temperature, can control the preparation time of the whole expanded graphite within 10 minutes, has simple and safe implementation process and is suitable for mass production.
Description
Technical Field
The invention relates to the technical field of graphite, in particular to expanded graphite and a preparation method and application thereof.
Background
The expanded graphite can be made into graphite paper by calendaring, can be used as an important precursor for preparing graphene, and attracts wide attention and research. Compared with pure graphite, the expanded graphite has larger apparent volume and weaker interlayer bonding force. The existing method for synthesizing expanded graphite mainly comprises a high-temperature expansion method and a chemical expansion method. The chemical expansion method is mainly prepared by intercalation reaction of a chemical reagent and a graphite compound, wherein the main expansion reagent is a persulfate expansion agent, and the research on a sulfuric acid intercalation graphite compound is more. However, the methods reported at present require heating or take several hours to prepare the expanded graphite.
Disclosure of Invention
In order to overcome the problems of the prior art, the first object of the present invention is to provide a method for preparing expanded graphite.
The second object of the present invention is to provide an expanded graphite prepared by the above preparation method.
The third invention of the present invention is to provide an application of the above expanded graphite in the preparation of graphene.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing expanded graphite, comprising the steps of:
s1: mixing phosphorus pentoxide, an expanding agent, graphite and sulfuric acid for reaction to prepare a mixture;
s2: and mixing the mixture with an expansion aid for reaction to prepare the expanded graphite.
Preferably, in the step S1, the mixing reaction temperature is 20-48 ℃; further preferably, in the step S1, the mixing reaction temperature is 20-35 ℃; still more preferably, in the step S1, the mixing reaction temperature is 25 to 35 ℃.
Preferably, in the step S1, the mixing reaction time is 1-10 min; further preferably, in the step S1, the mixing reaction time is 1 to 5 min; still more preferably, in the step S1, the mixing reaction time is 1 to 2 min.
Preferably, the swelling agent is a persulfate.
Preferably, the persulfate is selected from at least one of sodium persulfate, potassium hydrogen persulfate, ammonium persulfate, potassium persulfate, and magnesium persulfate. The expanding agent can intercalate graphite under the action of sulfuric acid, and can decompose in the sulfuric acid to generate gas, and the gas generated by the decomposition between graphite layers can overcome the pi-pi interaction between graphite sheets to expand the graphite to form expanded graphite; and a plurality of folds are formed on the surface of the expanded graphite, and the folds can be stretched or bent under the action of external stress, so that the prepared expanded graphite has good toughness.
Preferably, the mesh number of the graphite is 32-10000 meshes; more preferably, the mesh number of the graphite is 32-500 meshes; still more preferably, the mesh number of the graphite is 70 to 325 mesh.
Preferably, the step S1 is specifically: phosphorus pentoxide, an expanding agent, graphite and sulfuric acid are sequentially added into a reaction vessel for mixing and reacting. Adopt the application of sample order in this preferred scheme can avoid too early sulfur trioxide white smoke.
Preferably, the expansion aid is at least one selected from hydrogen peroxide and water.
Preferably, the mass-to-volume ratio of graphite to sulfuric acid is: 1: (10-100) g/mL; further preferably, the mass-to-volume ratio of graphite to sulfuric acid is: 1: (13-50) g/mL.
Preferably, the mass-to-volume ratio of the phosphorus pentoxide to the sulfuric acid is: (0.8-4): 10 g/mL; further preferably, the mass-to-volume ratio of the phosphorus pentoxide to the sulfuric acid is: (2-4): 10 g/mL.
Preferably, the mass fraction of the sulfuric acid is 95-98%; more preferably, the mass fraction of the sulfuric acid is 97% to 98%.
Preferably, the mass ratio of the graphite to the expanding agent is 1: (5-15); further preferably, the mass ratio of the graphite to the expanding agent is 1: (8-15).
Preferably, the step S2 further includes a step of washing after standing.
Preferably, the standing time of the standing step is 1-10 min; further preferably, the standing time of the standing step is 1-5 min; still further preferably, the standing time of the standing step is 1-3 min;
preferably, the water washing step is specifically washing with water to neutrality.
Preferably, the volume ratio of the swelling aid to the sulfuric acid is: (0.1-1): 10; further preferably, the volume ratio of the swelling aid to the sulfuric acid is: (0.2-1): 10; still further preferably, the volume ratio of the swelling aid to the sulfuric acid is: (0.2-0.5): 10.
a second aspect of the present invention provides an expanded graphite prepared by the above method.
Preferably, the expansion multiple of the expanded graphite is 20-200 ml/g; more preferably, the expansion multiple of the expanded graphite is 100-200 ml/g.
The third aspect of the invention provides an application of the expanded graphite in preparation of graphene.
The invention has the beneficial effects that: the method provided by the invention can synthesize the chemical expanded graphite, has controllable acid consumption, low energy consumption and simple and safe implementation process, and is suitable for mass production.
The method disclosed by the invention has the advantages that heating energy consumption is not needed, the reaction can be quickly carried out at the temperature of 20-48 ℃, the preparation time of the expanded graphite can be controlled within 10 minutes, the implementation process is simple and safe, and the method is suitable for mass production.
Drawings
FIG. 1 is a diagram showing the suspension of expanded graphite in water.
Fig. 2 is a Raman chart of expanded graphite.
FIG. 3 is an in situ Raman plot of intercalated graphite in different systems.
FIG. 4 is a scanning electron micrograph of expanded graphite taken at 100 times magnification.
FIG. 5 is a scanning electron micrograph of expanded graphite taken at 1000-fold magnification.
FIG. 6 is a scanning electron micrograph of expanded graphite magnified 20000 times.
Detailed Description
Specific embodiments of the present invention are described in further detail below with reference to the figures and examples, but the practice and protection of the present invention is not limited thereto. It is noted that the following processes, if not described in particular detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
The process for producing expanded graphite of this example comprises the steps of:
(1) sequentially adding 2g of phosphorus pentoxide, 5g of potassium persulfate and 1g of 32-mesh graphite into a beaker at the temperature of 31 ℃, quickly pouring 10ml of sulfuric acid, stirring and dissolving by using a glass rod, and reacting for 1 min;
(2) adding 1ml of hydrogen peroxide, quickly stirring, and standing for 1min at room temperature;
(3) adding 100ml of water at one time, washing to be neutral, and freeze-drying to obtain the expanded graphite.
Example 2
The process for producing expanded graphite of this example comprises the steps of:
(1) sequentially adding 4g of phosphorus pentoxide, 15g of potassium persulfate and 1g of 10000-mesh graphite into a beaker at the temperature of 31 ℃, quickly pouring 50ml of sulfuric acid, stirring and dissolving by using a glass rod, and reacting for 10 min;
(2) adding 1ml of hydrogen peroxide, quickly stirring, and standing at room temperature for 10 min;
(3) adding 200ml of water at one time, washing the mixture to be neutral, and freeze-drying the mixture to obtain the expanded graphite.
Example 3
The process for producing expanded graphite of this example comprises the steps of:
(1) sequentially adding 20g of phosphorus pentoxide, 15g of potassium persulfate and 1g of 10000-mesh graphite into a beaker at the temperature of 31 ℃, quickly pouring 50ml of sulfuric acid, stirring and dissolving by using a glass rod, and reacting for 10 min;
(2) adding 1ml of hydrogen peroxide, quickly stirring, and standing at room temperature for 10 min;
(3) adding 250ml of ice water at one time, washing with water to be neutral, and freeze-drying to obtain the expanded graphite.
Example 4
The process for producing expanded graphite of this example comprises the steps of:
(1) sequentially adding 3g of phosphorus pentoxide, 8g of potassium persulfate and 1g of 325-mesh graphite into a beaker at the temperature of 31 ℃, quickly pouring 13ml of sulfuric acid, stirring and dissolving by using a glass rod, and reacting for 2 min;
(2) adding 1ml of hydrogen peroxide, quickly stirring, and standing at room temperature for 5 min;
(3) adding 70ml of water at one time, washing the mixture to be neutral, and freezing and drying the mixture to obtain the expanded graphite.
Example 5
The process for producing expanded graphite of this example comprises the steps of:
(1) under the condition that the temperature is 31 ℃, 23g of phosphorus pentoxide, 8g of potassium persulfate and 1g of 325-mesh graphite are sequentially added into a beaker, 100ml of sulfuric acid is rapidly poured into the beaker, and a glass rod is stirred and dissolved to react for 2 min;
(2) adding 1ml of hydrogen peroxide, quickly stirring, and standing at room temperature for 5 min;
(3) adding 200ml of water at one time, washing the mixture to be neutral, and freeze-drying the mixture to obtain the expanded graphite.
Example 6
The process for producing expanded graphite of this example comprises the steps of:
(1) sequentially adding 3g of phosphorus pentoxide, 8g of potassium persulfate and 1g of 32-mesh graphite into a beaker at the temperature of 31 ℃, quickly pouring 13ml of sulfuric acid, stirring and dissolving by using a glass rod, and reacting for 2 min;
(2) adding 1ml of hydrogen peroxide, quickly stirring, and standing at room temperature for 5 min;
(3) adding 70ml of water at one time, washing the mixture to be neutral, and freezing and drying the mixture to obtain the expanded graphite.
Example 7
The process for producing expanded graphite of this example comprises the steps of:
(1) under the condition that the temperature is 31 ℃, 23g of phosphorus pentoxide, 8g of potassium persulfate and 1g of 32-mesh graphite are sequentially added into a beaker, 100ml of sulfuric acid is rapidly poured in, a glass rod is stirred and dissolved, and the reaction is carried out for 2 min;
(2) adding 1ml of hydrogen peroxide, quickly stirring, and standing at room temperature for 5 min;
(3) adding 200ml of water at one time, washing the mixture to be neutral, and freeze-drying the mixture to obtain the expanded graphite.
Example 8
The process for producing expanded graphite of this example comprises the steps of:
(1) sequentially adding 3g of phosphorus pentoxide, 8g of potassium persulfate and 1g of 70-mesh graphite into a beaker at the temperature of 31 ℃, quickly pouring 13ml of sulfuric acid, stirring and dissolving by using a glass rod, and reacting for 1 min;
(2) adding 1ml of hydrogen peroxide, quickly stirring, and standing at room temperature for 5 min;
(3) adding 200ml of water at one time, washing the mixture to be neutral, and freeze-drying the mixture to obtain the expanded graphite.
Example 9
The process for producing expanded graphite of this example comprises the steps of:
(1) sequentially adding 3g of phosphorus pentoxide, 8g of potassium persulfate and 1g of 70-mesh graphite into a beaker at the temperature of 31 ℃, quickly pouring 13ml of sulfuric acid, stirring and dissolving by using a glass rod, and reacting for 1 min;
(2) adding 1ml of water, rapidly stirring, and standing at room temperature for 5 min;
(3) adding 200ml of water at one time, washing the mixture to be neutral, and freeze-drying the mixture to obtain the expanded graphite.
Comparative example 1
The preparation process in comparative example 1 is substantially the same as example 8, with the only difference that: comparative example 1 no phosphorus pentoxide was added in step (1). The remaining steps were the same as in example 8 to prepare an expanded graphite.
Comparative example 2
The preparation in comparative example 2 is substantially the same as in example 8, with the only difference that: comparative example 2 in step (1), potassium persulfate was not added. The remaining steps were the same as in example 8 to prepare an expanded graphite.
Comparative example 3
Comparative example 3 was prepared in substantially the same manner as example 8, with the only difference that: comparative example 3 no hydrogen peroxide or water was added in step (2). The remaining steps were the same as in example 8 to prepare an expanded graphite.
Comparative example 4
Comparative example 4 was prepared in substantially the same manner as example 8, with the only difference that: comparative example 4 no phosphorus pentoxide was added in step (1), nor was hydrogen peroxide or water added in step (2). The remaining steps were the same as in example 8 to prepare an expanded graphite.
And (3) verifying the implementation effect:
the wet expanded graphite products of examples 1 to 9 and comparative examples 1 to 4 were suspended in water, and their apparent expansion volumes were measured by means of a measuring cup with a scale mark. The expansion factors of the expanded graphite prepared in examples 1 to 9 are shown in Table 1. The traditional thermal expansion method and the chemical expansion method are usually suitable for graphite with larger sheet diameter (smaller than 100 meshes), and the data in the examples 1-9 show that the preparation method of the expanded graphite provided by the invention is wider in applicable graphite sheet diameter range, the graphite with 32-10000 meshes is obviously expanded, and the expansion multiple is 10-190 ml/g. It is understood from examples 4, 5, 6 and 7 that the swelling effect is remarkably increased by increasing the amount of sulfuric acid and phosphorus pentoxide for small-diameter graphite, while the swelling effect is not remarkably increased by increasing the amount of sulfuric acid and phosphorus pentoxide for large-diameter graphite because the expansion agent is difficult to enter between the graphite layers due to the excessively large diameter of the graphite. Sulfuric acid has two functions in the present invention: firstly, the graphite layer spacing is increased by using the graphite as an intercalation agent, and simultaneously, the expansion aid is inserted between the graphite layers, and the graphite and the intercalation agent form first-order intercalation graphite together; secondly, sulfuric acid acts as a solvent to transfer more of the expansion agent into the graphite layers. The too small sheet diameter (10000 mesh) has a smaller apparent expansion factor, but the expansion still occurs compared to the original graphite, probably because the graphite is packed more densely. The expansion factors of the expanded graphite prepared in comparative examples 1 to 4 are shown in Table 2. As can be seen from table 2: the expansion effect is weakened to some extent without adding phosphorus pentoxide, only weak expansion occurs without adding potassium persulfate, the expansion effect is weakened without adding hydrogen peroxide, and the expansion effect is also weaker without adding phosphorus pentoxide and hydrogen peroxide.
TABLE 1 multiple of expansion of the expanded graphite prepared in examples 1 to 9
| |
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| Graphite mesh (mesh) | 32 | 10000 | 10000 | 325 | 325 | 32 | 32 | 70 | 70 |
| Sulfuric acid (ml) | 10 | 50 | 50 | 13 | 100 | 13 | 100 | 13 | 13 |
| Phosphorus pentoxide (g) | 2 | 4 | 20 | 3 | 23 | 3 | 23 | 3 | 3 |
| Potassium persulfate (g) | 5 | 15 | 15 | 8 | 8 | 8 | 8 | 8 | 8 |
| Pre-expansion time (min) | 1 | 10 | 10 | 2 | 2 | 2 | 2 | 1 | 1 |
| 30% dioxygenWater or Water (ml) | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1a |
| Swelling time (min) | 1 | 10 | 10 | 5 | 5 | 5 | 5 | 5 | 5 |
| Multiple of expansion (ml/g) | 100 | 30 | 50 | 100 | 190 | 160 | 150 | 140 | 150 |
TABLE 2 expansion factor of expanded graphite prepared in comparative examples 1 to 4
| Comparative example No. | 1 | 2 | 3 | 4 |
| Graphite mesh (mesh) | 70 | 70 | 70 | 70 |
| Sulfuric acid (ml) | 13 | 13 | 13 | 13 |
| Phosphorus pentoxide (g) | 0 | 3 | 3 | 0 |
| Potassium persulfate (g) | 8 | 0 | 8 | 8 |
| Pre-expansion time (min) | 1 | 1 | 1 | 1 |
| 30% hydrogen peroxide or water (ml) | 1b | 1b | 0 | 0 |
| Swelling time (min) | 5 | 5 | 5 | 5 |
| Multiple of expansion (ml/g) | 50 | 40 | 110 | 75 |
Note: a indicates that water is added, and b indicates that hydrogen peroxide is added.
The expanded graphite obtained by the preparation method of example 6 was prepared from 1g of graphite, and the expansion factor, raman data, scanning electron micrograph and the like of the expanded graphite were measured. First, when water is added to the expanded graphite, the suspension of the expanded graphite in water is shown in FIG. 1, which shows that the apparent density of the expanded graphite is less than 1g/cm3This indicates that the gas generated by the expansion remains between the graphite layers. The expanded graphite was characterized by Raman spectroscopy, as shown in FIG. 2, using an apparatus HJY LabRAM ARamis (Horiba Jobin Yvon) with a 532nm laser. FIG. 2 shows that: the obtained expanded graphite has a relatively symmetrical 2D peak. FIG. 3 shows intercalated stones of different systemsThe in-situ Raman diagram of the ink specifically comprises: (1) an in-situ Raman spectrum of a product obtained by referring to the production method in example 6 when graphite, sulfuric acid, phosphorus pentoxide, and potassium persulfate were contained in the reaction system; (2) an in-situ Raman spectrum of a product obtained by referring to the production method in example 6 when graphite, sulfuric acid and potassium persulfate were contained in the reaction system; (3) an in-situ Raman spectrum of a product obtained with reference to the production method in example 6 when graphite and sulfuric acid were contained in the reaction system; (4) in situ Raman plots of the blank control graphite. As can be seen in fig. 3: the G peak is shifted to the direction of high frequency number to represent the occurrence of intercalation, and the more the shift is, the more sufficient the intercalation is. The main function of the swelling agent in the present invention is to oxidize the intercalation agent and the swelling agent. The main function of phosphorus pentoxide is to enhance the acidity of the sulfuric acid, to enhance intercalation and expansion effects. The main functions of the hydrogen peroxide are a heating agent and an auxiliary expansion agent. The hydrogen peroxide is dissolved in the sulfuric acid and reacts with the sulfuric acid to form persulfuric acid, and simultaneously, a large amount of heat can be generated, so that the expanding agent existing between the graphite layers is rapidly decomposed, and the graphite can expand in a short time.
The scanning electron micrographs of the expanded graphite obtained from 1g of the above graphite were measured at 100 times, 1000 times and 20000 times, respectively, as shown in FIGS. 4 to 6, and as can be seen from FIG. 4, the expanded graphite was observed to be in the form of a strip or a lump when the expanded graphite was 100 times magnified. As can be seen from fig. 5, when the expanded graphite was enlarged 1000 times, it was observed that the edges of the expanded graphite were significantly exfoliated in an accordion-like manner. As can be seen from fig. 6, when the expanded graphite is enlarged by 20000 times, the exfoliated graphite sheets are soft, and air bubbles remain in part of the sheets, and cannot be discharged even in a vacuum environment, which also proves that the expanding agent participates in the intercalation of graphite and decomposition occurs between graphite layers.
The above embodiments are merely preferred embodiments of the present invention, which are intended to illustrate the present invention and not to limit the present invention, and those skilled in the art should understand that they can make various changes, substitutions, modifications, etc. without departing from the spirit and principle of the present invention.
Claims (10)
1. A preparation method of expanded graphite is characterized by comprising the following steps: the method comprises the following steps:
s1: mixing phosphorus pentoxide, an expanding agent, graphite and sulfuric acid for reaction to prepare a mixture;
s2: and mixing the mixture with an expansion aid for reaction to prepare the expanded graphite.
2. The process for producing expanded graphite according to claim 1, wherein: in the step S1, the mixing reaction temperature is 20-48 ℃.
3. The process for producing expanded graphite according to claim 1, wherein: in the step S1, the mixing reaction time is 1-10 min.
4. The process for producing expanded graphite according to claim 1, wherein: the swelling agent is persulfate.
5. The process for producing expanded graphite according to claim 1, wherein: the mesh number of the graphite is 32-10000 meshes.
6. The process for producing expanded graphite according to any one of claims 1 to 5, wherein: the step S1 specifically includes: phosphorus pentoxide, an expanding agent, graphite and sulfuric acid are sequentially added into a reaction vessel for mixing and reacting.
7. The process for producing expanded graphite according to claim 1, wherein: the expansion aid is at least one selected from hydrogen peroxide and water.
8. The process for producing expanded graphite according to claim 7, wherein: the volume ratio of the swelling assistant agent to the sulfuric acid is as follows: (0.1-1): 10.
9. Expanded graphite obtained by the production process according to any one of claims 1 to 8.
10. Use of the expanded graphite of claim 9 for the preparation of graphene.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114620739A (en) * | 2022-03-30 | 2022-06-14 | 浙江省地质矿产研究所 | Nano lamellar pyrophyllite powder and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634869A (en) * | 2012-01-05 | 2012-08-15 | 浙江大学 | Method for preparing high-strength conductive graphene fibers by dry spinning |
| CN112194125A (en) * | 2020-10-21 | 2021-01-08 | 哈尔滨理工大学 | Normal pressure low temperature expansion method for natural flake graphite |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634869A (en) * | 2012-01-05 | 2012-08-15 | 浙江大学 | Method for preparing high-strength conductive graphene fibers by dry spinning |
| CN112194125A (en) * | 2020-10-21 | 2021-01-08 | 哈尔滨理工大学 | Normal pressure low temperature expansion method for natural flake graphite |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114620739A (en) * | 2022-03-30 | 2022-06-14 | 浙江省地质矿产研究所 | Nano lamellar pyrophyllite powder and preparation method thereof |
| CN114620739B (en) * | 2022-03-30 | 2023-08-25 | 浙江省地质院 | Nanometer lamellar pyrophyllite powder and preparation method thereof |
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