CN108033440B - Preparation method of porous folded graphene with high specific surface area - Google Patents
Preparation method of porous folded graphene with high specific surface area Download PDFInfo
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- CN108033440B CN108033440B CN201810039873.1A CN201810039873A CN108033440B CN 108033440 B CN108033440 B CN 108033440B CN 201810039873 A CN201810039873 A CN 201810039873A CN 108033440 B CN108033440 B CN 108033440B
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Abstract
The invention provides a preparation method of porous wrinkled graphene with high specific surface area, which comprises the steps of mixing a graphene oxide solution and a water-soluble nitrogen-containing compound, reacting for a certain time at a certain temperature, and addingUniformly mixing the pore agents to obtain a mixed solution; ultrasonically atomizing the mixed solution and heating at a certain temperature to volatilize the solvent in the mixed solution to obtain graphene oxide/pore-forming agent powder particles; collecting the obtained graphene oxide/pore-forming agent powder particles and carrying out heat treatment under the protection of inert gas to obtain a folded graphene product with a high specific surface area, wherein the heat treatment temperature is 600-1100 ℃, and the pore-forming agents are NaOH, KOH and K2CO3Etc., the specific surface area of the obtained product is 1000 to 2000m2Between/g. The method can obtain high specific surface area while maintaining the morphology of the folded graphene.
Description
Technical Field
The invention belongs to the field of chemical industry, relates to graphene, and particularly relates to a preparation method of porous folded graphene with a high specific surface area.
Background
The graphene is sp2Two-dimensional honeycomb crystals composed of hybridized carbon atoms. Theoretically, the two-dimensional graphene has an ultra-high specific surface area, good conductivity, high carrier mobility, high mechanical strength and the like, so that the two-dimensional graphene is concerned in the application of two-dimensional materials. At present, one obstacle to the industrial application of graphene materials is that van der waals force exists between graphene sheets, so that aggregation easily occurs between layers, which greatly reduces the specific surface area of the graphene, and limits the performance and application of the graphene. One possible approach is to convert the two-dimensional nanosheet structure into a three-dimensional, folded, conglomerated structure. Unlike flat sheets, graphene with a highly wrinkled bulk structure has a very high free volume and excellent compression resistance.
The wrinkle graphene is subjected to pore forming, so that the specific surface area of the wrinkle graphene is further improved while the wrinkle morphology of the wrinkle graphene is maintained, and the performance of the wrinkle graphene is improved. However, the folded graphene is directly activated by the pore-forming agent, and although a high specific surface area is obtained, the folded structure is completely lost. Porous wrinkled graphene can be prepared by simultaneously spraying graphene oxide and a pore-forming agent for wrinkling, but the commonly used pore-forming agent usually has reducibility and can partially reduce the graphene oxide, so that the acting force between solvent water and the graphene oxide in the spray drying process is changed, the reduced graphene oxide can be partially stacked, and the specific surface area of the prepared porous wrinkled graphene is low and is generally lower than 1000m2Per g, thus preparing a high specific surface areaThe porous folded graphene has important practical significance for widening the practical application of graphene.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a preparation method of porous folded graphene with high specific surface area, which is connected with the technical problem that the specific surface area of the prepared porous folded graphene in the prior art is relatively low.
The invention provides a preparation method of porous folded graphene with high specific surface area, which comprises the following steps:
1) mixing a graphene oxide solution and a water-soluble nitrogen-containing compound, wherein the concentration of the graphene oxide solution is 0.1-5mg/ml, the water-soluble nitrogen-containing compound is selected from any one of ammonia water, ethylenediamine, aniline, triethylene tetramine or tetraethylene pentamine, the mass ratio of the water-soluble nitrogen-containing compound to the graphene oxide is 1:10-100:1, reacting for 0.1-24h at the temperature of 0-100 ℃, and then adding a pore-forming agent and uniformly mixing to obtain a mixed solution; the pore-forming agent is NaOH, KOH or K2CO3The mass ratio of the graphene oxide to the pore-forming agent is 1:1-1: 5;
2) carrying out ultrasonic atomization on the mixed solution, and heating at the temperature of 100-600 ℃ to obtain graphene oxide/pore-forming agent powder particles;
3) carrying out heat treatment on the graphene oxide/pore-forming agent powder particles under the protection of inert gas, wherein the heat treatment temperature is 400-1100 ℃, obtaining the porous folded graphene with the high specific surface area, and the specific surface area of the obtained porous folded graphene with the high specific surface area is 1000-2000 m2Between/g.
Further, in the step 1), mixing the graphene oxide solution and ammonia water according to a mass ratio of 1:10, reacting for 6 hours at 60 ℃, and then adding a catalyst which is mixed with graphene oxide according to a mass ratio of 4:1 KOH, and evenly mixing to obtain a mixed solution.
The method comprises the steps of mixing a graphene oxide solution with a water-soluble nitrogen-containing compound and other hydrophilic reducing agents, reacting for a certain time at a certain temperature, adding a pore-forming agent, and uniformly mixing to obtain a mixed solution; ultrasonically atomizing the mixed solution and heating at a certain temperature to volatilize the solvent in the mixed solution to obtain graphene oxide/pore-forming agent powder particles; and collecting the obtained graphene oxide/pore-forming agent powder particles and carrying out heat treatment under the protection of inert gas to obtain a high-specific-surface-area folded graphene product.
According to the invention, firstly, graphene oxide is reduced by using a hydrophilic nitrogen-containing compound, and then a pore-forming agent is added for ultrasonic atomization treatment on the premise of keeping the hydrophilic property of the graphene oxide, so that the agglomeration of the reduced graphene oxide is reduced, and the porous folded graphene with high specific surface area is obtained.
According to the invention, the water-soluble nitrogen-containing compound is mixed with the graphene oxide solution, so that the hydrophilicity of the graphene oxide solution can be maintained by the colleagues who partially reduce the graphene oxide, and a stable solution can be formed after the pore-forming agent is added, thereby facilitating the ultrasonic atomization treatment of the graphene oxide solution.
Compared with the prior art, the invention has remarkable technical progress. According to the invention, the graphene oxide is pretreated by the nitrogen-containing compound to ensure that the graphene oxide is reduced and the hydrophilicity is kept, and then the added pore-forming agent (such as KOH, NaOH and the like) with reducing performance can not further reduce the primarily reduced graphene oxide, so that the reduced graphene oxide is ensured to have good hydrophilicity and monodispersity, and the method is a key step for preparing the folded graphene with high specific surface area.
Drawings
Fig. 1 is a topography of porous corrugated graphene prepared according to the method of the invention in example 1.
Fig. 2 is a topography of porous corrugated graphene prepared according to the method of the invention in example 2.
Fig. 3 is a morphology chart of porous corrugated graphene prepared according to the method of the invention in example 3.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
Example 1
Taking 400ml of 1mg/ml graphene oxide solution, firstly adding 30ml of ammonia water with the mass percentage concentration of 25%, reacting for 5h at 30 ℃, and then addingAdding sodium hydroxide, wherein the mass ratio of the sodium hydroxide to the graphene oxide is 2:1, uniformly mixing, carrying out ultrasonic atomization treatment, drying at 500 ℃, carrying out heat treatment on the collected sample at 800 ℃ for 1 hour under the protection of nitrogen, and washing to be neutral. Finally obtaining porous folded graphene with specific surface area of 1100m2(ii) in terms of/g. The morphology of the porous corrugated graphene is shown in fig. 1.
Example 2
Taking 200ml of 3mg/ml graphene oxide solution, firstly adding 6g of anhydrous ethylenediamine, reacting at 80 ℃ for 12h, then adding potassium hydroxide, wherein the mass ratio of potassium hydroxide to graphene oxide is 4:1, uniformly mixing, carrying out ultrasonic atomization treatment, drying at 300 ℃, carrying out heat treatment on the collected sample at 700 ℃ for 2h under the protection of nitrogen, and washing to be neutral. Finally obtaining porous folded graphene with specific surface area of 1636m2(ii) in terms of/g. The morphology of the porous corrugated graphene is shown in fig. 2.
Example 3
Taking 300ml of 2mg/ml graphene oxide solution, firstly adding 30g of tetraethylenepentamine, reacting for 20h at 100 ℃, then adding potassium carbonate, wherein the mass ratio of the potassium carbonate to the graphene oxide is 3:1, uniformly mixing, carrying out ultrasonic atomization treatment, drying at 600 ℃, carrying out heat treatment on the collected sample at 1000 ℃ for 2h under the protection of nitrogen, and washing to be neutral. Finally obtaining porous folded graphene with the specific surface area of 1218m2(ii) in terms of/g. The morphology of the porous corrugated graphene is shown in fig. 3.
Claims (2)
1. A preparation method of porous folded graphene with high specific surface area is characterized by comprising the following steps:
1) mixing a graphene oxide solution and a water-soluble nitrogen-containing compound, wherein the concentration of the graphene oxide solution is 0.1-5mg/ml, the water-soluble nitrogen-containing compound is selected from any one of ammonia water, ethylenediamine, aniline, triethylene tetramine or tetraethylene pentamine, the mass ratio of the water-soluble nitrogen-containing compound to the graphene oxide is 1:10-100:1, reacting for 0.1-24h at the temperature of 0-100 ℃, and then adding a pore-forming agent and uniformly mixing to obtain a mixed solution; the pore-forming agent is NaOH, KOH or K2CO3Of graphene oxide with pore-forming agentThe mass ratio is 1:1-1: 5;
2) carrying out ultrasonic atomization on the mixed solution, and heating at the temperature of 100-600 ℃ to obtain graphene oxide/pore-forming agent powder particles;
3) carrying out heat treatment on the graphene oxide/pore-forming agent powder particles under the protection of inert gas, wherein the heat treatment temperature is 400-1100 ℃, obtaining the porous folded graphene with the high specific surface area, and the specific surface area of the obtained porous folded graphene with the high specific surface area is 1000-2000 m2Between/g.
2. The preparation method of porous corrugated graphene with high specific surface area according to claim 1, wherein the preparation method comprises the following steps: in the step 1), mixing a graphene oxide solution and ammonia water according to a mass ratio of 1:10, reacting for 6 hours at 60 ℃, and then adding a catalyst which is mixed with graphene oxide according to a mass ratio of 4:1 KOH, and evenly mixing to obtain a mixed solution.
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| CN113233448B (en) * | 2021-06-10 | 2022-04-08 | 北京航空航天大学 | Surface modification method for reduced graphene oxide |
| CN114497513A (en) * | 2022-03-05 | 2022-05-13 | 青岛泰达华润新能源科技有限公司 | Graphene negative electrode material for lithium ion battery and preparation method thereof |
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