CN111573659A - Preparation method of nitrogen-doped graphene - Google Patents
Preparation method of nitrogen-doped graphene Download PDFInfo
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Abstract
The invention discloses a preparation method of nitrogen-doped graphene, which comprises the following steps: firstly, carrying out heat treatment on graphite powder in a nitrogen-containing active atmosphere to carry out nitridation and expansion to obtain nitrogen-doped graphite; and dispersing the nitrogen-doped graphite in a solvent, performing ultrasonic dispersion and centrifugation, and collecting supernatant to obtain the nitrogen-doped graphene material. The method of the invention can not introduce structural defects such as holes, chemical groups and the like into the graphene sheet layer, and the prepared nitrogen-doped graphene has the advantages of complete sheet layer, few defects, high nitrogen content, stable structure and the like.
Description
Technical Field
The invention relates to the technical field of graphene materials, in particular to a preparation method of nitrogen-doped graphene.
Background
Graphene is a novel two-dimensional crystal material formed by arranging six-membered rings of carbon atoms. Since the scientists at Manchester university in England discovered in 2004, the material has many advantages such as ultra-high specific surface area, excellent mechanical, electrical, optical, thermal and multifunctional properties, and has important research value and application prospect in the fields of energy, electronics, environment and the like.
People try to improve and regulate the structure and the performance of the graphene through various chemical modification methods, and particularly chemical element doping can greatly improve the structure and the performance of the graphene. The nitrogen atoms have similar atomic sizes to the carbon atoms, and are very easy to be combined into a carbon-carbon skeleton of graphene instead of the carbon atoms. Meanwhile, due to the high electronegativity of the nitrogen atom, lone pair electrons combined with the carbon atom can form a conjugated system with pi bond electrons of the carbon layer, so that the electronic characteristics and chemical activity of the graphene can be effectively improved, and the graphene has more important and wider application in the functional fields of micro-nano electronic devices, catalysis, electrochemistry, sensing and the like.
At present, the common method for preparing nitrogen-doped graphene is to synthesize graphene oxide first and then carry out nitrogen doping by subsequent methods such as high-temperature heating, solvothermal, nitrogen plasma discharge, microwave irradiation and the like. However, these subsequent nitrogen doping methods have disadvantages that the introduced nitrogen component is difficult to form a stable bonding structure inside the carbon layer, and simultaneously a large amount of void defects and unnecessary oxygen groups are introduced into the graphene carbon layer, thereby seriously affecting the performance and structural stability of graphene; and also directly synthesizing the nitrogen-doped graphene by using a precursor containing carbon and nitrogen as a carbon source and a nitrogen source through a chemical vapor deposition or arc discharge method. However, these methods involve complicated processes such as treatment of growth substrate, separation and transfer of graphene film, and these processes are harsh, have very high requirements on equipment and cost, and are difficult to scale up.
Therefore, how to provide a method for preparing nitrogen-doped graphene with low defects, low cost, high quality, simple process, high speed and high efficiency is a problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a preparation method of nitrogen-doped graphene, which has the advantages of low cost, good quality, few defects, simple preparation process, rapidness and high efficiency, aiming at the defects of the prior art.
The preparation method of the nitrogen-doped graphene provided by the invention is completely different from the prior subsequent nitrogen doping method and the direct nitrogen doping method, and nitrogen elements are directly doped into the graphite powder raw material, and the nitrogen-doped graphene is prepared by processes such as ultrasonic stripping. The nitrogen-doped graphene prepared by the method has few defects, no oxygen group is introduced, the sheet layer is complete, nitrogen atoms are stably combined in the graphene carbon layer, and the number of graphene layers is few.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of nitrogen-doped graphene comprises the following steps:
(1) heat-treating graphite powder in nitrogen-containing active atmosphere to dope nitrogen element into the graphite layer and expand graphite;
(2) and (2) dispersing the nitrogen-doped graphite powder obtained in the step (1) in a solvent, and collecting supernatant through ultrasonic dispersion and centrifugation to obtain the nitrogen-doped graphene material.
Preferably, in the above preparation method of nitrogen-doped graphene, the graphite powder in step (1) is one of natural flaky graphite, cracked expanded graphite, or other lamellar graphite powder which is not chemically modified.
The beneficial effects of the above technical scheme are: the natural flaky graphite and the cracked expanded graphite are widely and easily available in source, and the flaky graphite powder which is not chemically modified is used as a raw material, so that the introduction of additional chemical reaction in the high-temperature pre-nitriding and stripping processes can be avoided, and the integrity of the graphite layer structure is ensured.
Preferably, in the preparation method of nitrogen-doped graphene, the nitrogen-containing active atmosphere in step (1) is one of ammonia gas, a mixed gas of ammonia gas and argon gas, a mixed gas of ammonia gas and helium gas, a mixed gas of ammonia gas and nitrogen gas, and a mixed gas of ammonia gas and hydrogen gas.
The beneficial effects of the above technical scheme are: the invention adopts ammonia gas as a nitrogen source, but not a nitrogen-containing organic matter which is commonly used in the past, because the ammonia gas as reducing gaseous micromolecules can be effectively diffused and infiltrated among carbon layers, and decompose nitrogen atoms at a certain heat treatment temperature to dope the carbon layers, and meanwhile, the decomposed micromolecule gas can be discharged along with airflow, and other components such as oxygen groups and the like can not be introduced into the carbon layers.
Preferably, in the preparation method of nitrogen-doped graphene, in the step (1), the heat treatment temperature is 500-.
The beneficial effects of the above technical scheme are: the experimental result proves that the nitrogen atom doping can be realized under the pre-nitridation condition. The graphite powder is subjected to pre-nitridation treatment for 0.5h at the temperature of over 500 ℃, nitrogen atoms decomposed from ammonia gas can be effectively combined into a carbon-carbon skeleton to realize nitrogen atom doping, and the content of the nitrogen atoms reaches 1.0%; and as the heat treatment temperature is increased and the heat treatment time is increased, the content of nitrogen atoms in the graphene product is gradually increased.
Preferably, in the above method for preparing nitrogen-doped graphene, the solvent in step (2) is an organic solvent having wettability with the surface of graphene, or the solvent is an ionic aqueous solution having intercalation effect on graphite layer.
The beneficial effects of the above technical scheme are: the graphitic carbon layer exhibits a typical non-polarity on its surface due to the covalent bond structure between carbon atoms and is therefore difficult to disperse directly in water. On one hand, the nitrogen-doped graphite powder is dispersed into an organic solvent with similar nonpolar performance to the surface of graphene, and the surface energy of the graphene is reduced through high-energy oscillation in ultrasonic dispersion, so that a carbon layer is gradually stripped and dispersed into the solvent to form the graphene; on the other hand, the nitrogen-doped graphite powder is dispersed into an ionic aqueous solution, and the carbon layer is intercalated and peeled in the ultrasonic process by utilizing small-size ions and the electrostatic charge action between surfactant molecules and graphene sheet layers, so that the carbon layer is separated and dispersed into a solvent to form graphene. By utilizing the technical scheme, the carbon layer can be simply, conveniently and quickly stripped to obtain the nitrogen-doped graphene material.
Preferably, in the above method for preparing nitrogen-doped graphene, the solvent is N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, tetrahydrofuran, propanol, isopropanol, ethylene glycol, ethanol, acetone, nitromethane, toluene, polyvinylpyrrolidone/N, N-dimethylformamide solution, polyvinylpyrrolidone/N, N-dimethylacetamide solution, polyvinylpyrrolidone/N-methylpyrrolidone solution, polyvinylpyrrolidone/dimethyl sulfoxide solution, polyvinylpyrrolidone/N, N-tetrahydrofuran solution, polyvinylpyrrolidone/propanol solution, polyvinylpyrrolidone/isopropanol solution, polyvinylpyrrolidone/ethylene glycol solution, or a mixture thereof, One of polyvinylpyrrolidone/ethanol solution and polyvinylpyrrolidone/nitromethane solution.
Preferably, in the preparation method of nitrogen-doped graphene, the solvent is one of aqueous solutions of hydrogen chloride, phosphoric acid, lithium chlorate, lithium perchlorate, potassium chloride, potassium perchlorate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium lauryl sulfate, and sodium fatty alcohol ether sulfate.
Preferably, in the above method for preparing nitrogen-doped graphene, the dispersion concentration of the nitrogen-doped graphite powder in the solvent in the step (2) is 0.01-2.0 mg/mL. The concentration of the nitrogen-doped graphite powder in the solvent is not high enough to avoid affecting the dispersibility and generating agglomeration.
Preferably, in the preparation method of nitrogen-doped graphene, the power of ultrasonic dispersion in the step (2) is 40-300W, the ultrasonic frequency is 40-60kHz, and the ultrasonic time is 1-48 h.
Preferably, in the preparation method of nitrogen-doped graphene, the rotation speed of the centrifugation in the step (2) is 5000-. And separating the product at a higher centrifugal speed, so that a monolayer or few-layer nitrogen-doped graphene product can be obtained as far as possible.
According to the technical scheme, compared with the prior art, the preparation method of the nitrogen-doped graphene disclosed by the invention has the following obvious technical advantages and effects:
(1) the nitrogen-doped graphene prepared by the method can not introduce structural defects such as holes and chemical groups into a graphene sheet layer, and has the advantages of few defects, complete sheet layer structure, high nitrogen atom content, stable structure and few graphene layers;
(2) the nitrogen-doped graphene obtained by the method is uniformly dispersed in the solvent, the problems of agglomeration and the like do not exist, and the method is more beneficial to compounding the graphene with other materials.
(3) The preparation method of the nitrogen-doped graphene provided by the invention has the advantages of very simple process, fast and efficient preparation process, low requirements on raw materials and equipment, low cost and suitability for large-scale mass production and application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Figure 1 accompanying drawing is a TEM photograph of nitrogen-doped graphene sheets prepared in example 1;
FIG. 2 is a high resolution TEM image of the edge of a nitrogen-doped graphene sheet prepared in example 1;
FIG. 3 is an EDS spectrum of nitrogen-doped graphite prepared in example 1;
FIG. 4 is an EDS spectrum of nitrogen-doped graphite prepared in example 2;
FIG. 5 is an EDS spectrum of nitrogen-doped graphite prepared in example 3;
figure 6 is an EDS spectrum of nitrogen-doped graphite prepared in example 4.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Placing natural flaky graphite (325 meshes) in a crucible, introducing argon into a vacuum tube furnace at the flow rate of 0.15L/min to remove air in the furnace tube, introducing ammonia at the flow rate of 0.1L/min, heating to 900 ℃ at the speed of 5 ℃/min, carrying out heat preservation and heat treatment for 5h to carry out nitridation and expansion, and introducing argon for 0.5h after the reaction furnace naturally cools to room temperature to obtain the nitrogen-doped graphite. Dispersing nitrogen-doped graphite in N, N-dimethylformamide with the concentration of 0.5mg/mL, and ultrasonically dispersing the nitrogen-doped graphite for 6 hours under the power of 100W and the frequency of 40 kHz; and then centrifuging the dispersion liquid for 5min at 10000rpm, namely about 10000 Xg centrifugal force, and sucking supernatant liquid by a suction pipe to obtain the nitrogen-doped graphene.
As shown in a TEM photograph of fig. 1, the nitrogen-doped graphene sheet prepared in example 1 has a complete structure, and the size distribution of the graphene sheet is 500nm-20 μm; as shown in fig. 2, no obvious void defect exists in the graphene sheet, and it can be seen from the edge of the graphene sheet that the single graphene contains only a few layers of graphite, which is a typical graphene structure. As shown in FIG. 3, the results of the spectrum analyzer showed that the nitrogen content was 14.77%. It should be noted that nitrogen elements contained in the N, N-dimethylformamide solvent in the above preparation process may be adsorbed on the surface of the graphite layer, thereby interfering with the nitrogen element content test result. Therefore, the energy spectrum analyzer is used for detecting the nitrogen doping content in the nitrogen-doped graphite in advance, and the detection result can accurately reflect the content of the nitrogen atoms doped in the graphene sheet layer. Unless otherwise specified, the method is adopted for the characterization of the nitrogen element content in other examples. The result shows that the nitrogen-doped graphene can be successfully prepared by the method.
Example 2
Placing natural flaky graphite (325 meshes) in a crucible, introducing argon into a vacuum tube furnace at the flow rate of 0.15L/min to remove air in the furnace tube, introducing ammonia at the flow rate of 0.6L/min, heating to 500 ℃ at the flow rate of 2 ℃/min, performing heat preservation and heat treatment for 12h to perform nitridation and expansion, and introducing argon for 0.5h after the reaction furnace naturally cools to room temperature to obtain the nitrogen-doped graphite. Dispersing nitrogen-doped graphite in ethanol with the concentration of 0.05mg/mL, and ultrasonically dispersing the nitrogen-doped graphite for 24 hours under the power of 300W and the frequency of 60 kHz; and then centrifuging the dispersion liquid for 5min at 10000rpm, namely about 10000 Xg centrifugal force, and sucking supernatant liquid by a suction pipe to obtain the nitrogen-doped graphene.
As shown in fig. 4, the results of the spectrum analyzer test showed that the nitrogen content was 10.65%.
Example 3
Placing natural flaky graphite (325 meshes) in a crucible, introducing argon into a vacuum tube furnace at the flow rate of 0.15L/min to remove air in the furnace tube, introducing ammonia at the flow rate of 0.1L/min, heating to 700 ℃ at the speed of 5 ℃/min, carrying out heat preservation and heat treatment for 5h to carry out nitridation and expansion, and introducing argon for 0.5h after the reaction furnace naturally cools to room temperature to obtain the nitrogen-doped graphite. Dispersing nitrogen-doped graphite in tetrahydrofuran with the concentration of 0.5mg/mL, and ultrasonically dispersing the graphite for 6 hours under the power of 100W and the frequency of 40 kHz; and then centrifuging the dispersion liquid for 5min at 10000rpm, namely about 10000 Xg centrifugal force, and sucking supernatant liquid by a suction pipe to obtain the nitrogen-doped graphene.
As shown in fig. 5, the results of the spectrum analyzer showed a nitrogen content of 12.99%.
Example 4
Placing natural flaky graphite (325 meshes) in a crucible, introducing argon into a vacuum tube furnace at the flow rate of 0.15L/min to remove air in the furnace tube, introducing ammonia at the flow rate of 0.1L/min, heating to 1200 ℃ at the speed of 20 ℃/min, performing heat preservation and heat treatment for 0.5h to perform nitridation and expansion, naturally cooling the reaction furnace to room temperature, and introducing argon for 0.5h to obtain the nitrogen-doped graphite. Dispersing nitrogen-doped graphite into a mixed solvent of polyvinylpyrrolidone/N, N-dimethylformamide solution, wherein the concentration of the mixed solvent is 2.0mg/mL, and ultrasonically dispersing the mixed solvent for 6 hours under the power of 100W and the frequency of 40 kHz; and then centrifuging the dispersion liquid for 5min at 10000rpm, namely about 10000 Xg centrifugal force, and sucking supernatant liquid by a suction pipe to obtain the nitrogen-doped graphene.
As shown in fig. 6, the results of the spectrum analyzer showed a nitrogen content of 16.22%.
Example 5
Placing natural flaky graphite (8000 meshes) in a crucible, introducing argon into a vacuum tube furnace at the flow rate of 0.15L/min to remove air in the furnace tube, introducing mixed gas of ammonia and argon (the volume fraction of the ammonia is 10%) at the flow rate of 0.1L/min, heating to 900 ℃ at the speed of 5 ℃/min, carrying out heat preservation and heat treatment for 5 hours to carry out nitridation and expansion, and introducing argon for 0.5 hour after the reaction furnace naturally cools to room temperature to obtain the nitrogen-doped graphite. Dispersing nitrogen-doped graphite in N-methylpyrrolidone, wherein the concentration is 0.5mg/mL, and ultrasonically dispersing the nitrogen-doped graphite for 6 hours under the power of 40W and the frequency of 40 kHz; and then centrifuging the dispersion liquid for 15min at the rotating speed of 16000rpm, namely under the centrifugal force of about 18000 Xg, and sucking the supernatant liquid by using a suction pipe to obtain the nitrogen-doped graphene.
Example 6
Putting commercial high-temperature cracked graphite into a crucible, introducing argon into a vacuum tube furnace at the flow rate of 0.15L/min to remove air in the furnace tube, introducing mixed gas of ammonia and nitrogen (the volume fraction of the ammonia is 50%) at the flow rate of 0.6L/min, heating to 900 ℃ at the speed of 5 ℃/min, carrying out heat preservation and heat treatment for 5 hours to carry out nitridation and expansion, and introducing argon for 0.5 hour after the reaction furnace naturally cools to room temperature to obtain the nitrogen-doped graphite. Dispersing nitrogen-doped graphite in polyvinylpyrrolidone/N-methyl pyrrolidone with the concentration of 0.5mg/mL, and ultrasonically dispersing the nitrogen-doped graphite for 6 hours under the power of 100W and the frequency of 40 kHz; and then centrifuging the dispersion liquid for 5min at 10000rpm, namely about 10000 Xg centrifugal force, and sucking supernatant liquid by a suction pipe to obtain the nitrogen-doped graphene.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the technical scheme disclosed by the embodiment, the method corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for explanation.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of nitrogen-doped graphene is characterized by comprising the following steps:
(1) heat-treating graphite powder in nitrogen-containing active atmosphere to dope nitrogen element into the graphite layer and expand graphite;
(2) and (2) dispersing the nitrogen-doped graphite powder obtained in the step (1) in a solvent, and collecting supernatant through ultrasonic dispersion and centrifugation to obtain the nitrogen-doped graphene material.
2. The method for preparing nitrogen-doped graphene according to claim 1, wherein the graphite powder in the step (1) is one of natural flaky graphite, cracked expanded graphite or other lamellar graphite powder without any chemical modification.
3. The method according to claim 1, wherein the nitrogen-doped active atmosphere in step (1) is one of ammonia gas, a mixed gas of ammonia gas and argon gas, a mixed gas of ammonia gas and helium gas, a mixed gas of ammonia gas and nitrogen gas, and a mixed gas of ammonia gas and hydrogen gas.
4. The method as claimed in claim 1, wherein the heat treatment temperature in step (1) is 500-1200 ℃, the temperature rise rate is 2-20 ℃/min, the gas flow rate is 0.06-0.6L/min, and the heat treatment time is 0.5-12 h.
5. The method according to claim 1, wherein the solvent in step (2) is an organic solvent having wettability with the surface of graphene, or the solvent is an ionic aqueous solution having intercalation effect on graphite layer.
6. The method according to claim 1 or 5, wherein the solvent is N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, tetrahydrofuran, propanol, isopropanol, ethylene glycol, ethanol, acetone, nitromethane, toluene, polyvinylpyrrolidone/N, N-dimethylformamide solution, polyvinylpyrrolidone/N, N-dimethylacetamide solution, polyvinylpyrrolidone/N-methylpyrrolidone solution, polyvinylpyrrolidone/dimethyl sulfoxide solution, polyvinylpyrrolidone/N, N-tetrahydrofuran solution, polyvinylpyrrolidone/propanol solution, polyvinylpyrrolidone/isopropanol solution, or a mixture thereof, One of polyvinylpyrrolidone/ethylene glycol solution, polyvinylpyrrolidone/ethanol solution, and polyvinylpyrrolidone/nitromethane solution.
7. The method according to claim 1 or 5, wherein the solvent is one of aqueous solutions of hydrogen chloride, phosphoric acid, lithium chlorate, lithium perchlorate, potassium chloride, potassium perchlorate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, and sodium fatty alcohol ether sulfate.
8. The method according to claim 1, wherein the dispersing concentration of the nitrogen-doped graphite powder in the solvent in the step (2) is 0.01-2.0 mg/mL.
9. The preparation method of nitrogen-doped graphene according to claim 1, wherein the power of ultrasonic dispersion in the step (2) is 40-300W, the ultrasonic frequency is 40-60kHz, and the ultrasonic time is 1-48 h.
10. The method as claimed in claim 1, wherein the rotation speed of the centrifugation in step (2) is 5000-16000rpm, the centrifugal force is 5000-18000 Xg, and the centrifugation time is 1-15 min.
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| CN102034975A (en) * | 2010-11-15 | 2011-04-27 | 中国科学院青岛生物能源与过程研究所 | Nitrogen-doped graphite carbon serving as anode material of lithium ion battery, and preparation method and application thereof |
| CN103553027A (en) * | 2013-10-23 | 2014-02-05 | 南京大学 | Method for preparing high-content nitrogen-doped graphene from fluorinated graphene |
| CN103803539A (en) * | 2014-02-17 | 2014-05-21 | 上海交通大学 | Nitrogen-doped graphene oxide material and preparation method thereof |
| KR20160114372A (en) * | 2015-03-24 | 2016-10-05 | 전남대학교산학협력단 | A method for producing graphene with rapid expansion and graphene made thereby |
| CN108658064A (en) * | 2018-08-08 | 2018-10-16 | 广东电网有限责任公司 | A kind of nitrogen-doped graphene and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102034975A (en) * | 2010-11-15 | 2011-04-27 | 中国科学院青岛生物能源与过程研究所 | Nitrogen-doped graphite carbon serving as anode material of lithium ion battery, and preparation method and application thereof |
| CN103553027A (en) * | 2013-10-23 | 2014-02-05 | 南京大学 | Method for preparing high-content nitrogen-doped graphene from fluorinated graphene |
| CN103803539A (en) * | 2014-02-17 | 2014-05-21 | 上海交通大学 | Nitrogen-doped graphene oxide material and preparation method thereof |
| KR20160114372A (en) * | 2015-03-24 | 2016-10-05 | 전남대학교산학협력단 | A method for producing graphene with rapid expansion and graphene made thereby |
| CN108658064A (en) * | 2018-08-08 | 2018-10-16 | 广东电网有限责任公司 | A kind of nitrogen-doped graphene and preparation method thereof |
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