CN115520858A - Preparation method of nitrogen-doped single-layer graphene - Google Patents
Preparation method of nitrogen-doped single-layer graphene Download PDFInfo
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- CN115520858A CN115520858A CN202210649885.2A CN202210649885A CN115520858A CN 115520858 A CN115520858 A CN 115520858A CN 202210649885 A CN202210649885 A CN 202210649885A CN 115520858 A CN115520858 A CN 115520858A
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Abstract
The invention discloses a preparation method of nitrogen-doped single-layer graphene, and provides a green method for preparing high-quality graphene based on chemical reaction bubble cleavage of graphite, aiming at the problem that the efficiency, safety and environmental friendliness cannot be considered when the high-quality graphene is prepared by cleaving graphite by using a traditional intercalation stripping method. Particularly, the method provided by the invention is combined with intermediate product analysis and comparison experiments to explore the preparation mechanism of high-quality graphene and regulate the importance of the bubble cleavage process, and through more than one hundred times of solution selection and experiments, the oxalic acid is innovatively selected as the electrolyte, so that the green, pollution-free and efficient graphene preparation is realized, the expenditure in the aspect of pollution treatment is greatly reduced, the yield is up to more than 95%, and the production cost is greatly reduced. The method can realize pollution-free preparation on the premise of mass production, and the prepared nitrogen-doped single-layer graphene realizes the improvement of the performance of the graphene and embodies some remarkable electrical properties.
Description
Technical Field
The invention relates to a preparation method of single-layer graphene, in particular to a preparation method of nitrogen-doped single-layer graphene.
Background
From 1840, scientists at home and abroad begin to research the graphite exfoliation technology, and the result is that graphene exfoliation is difficult to realize and that single-layer graphene exfoliation is more difficult to realize at present. The existing preparation technology has the disadvantages of high environmental pollution, extremely low yield and high cost, the number of layers of the produced graphene powder and the like restricts the application field of the graphene powder, and the 90 percent of single-layer graphene powder in China depends on import. By the year 2021, the single-layer graphene powder cannot be produced in large scale. Therefore, on the premise of ensuring the cleavage efficiency, the new intercalation and exfoliation method is designed to ensure that the preparation conditions are milder, the process is more environment-friendly, and the cost is lower, so that the intercalation-exfoliation method really surpasses other methods, becomes the key of a preferred scheme for preparing high-quality graphene, and is also an important direction for the preparation research of the existing graphene material.
Disclosure of Invention
The invention aims to solve the main technical problems that: aiming at the problem that the efficiency, the safety and the environmental protection can not be considered when the high-quality graphene is prepared by cleaving graphite by the traditional intercalation stripping method, a green method for preparing the high-quality graphene by cleaving graphite based on chemical reaction bubbles is provided. Specifically, the feasibility of the method is demonstrated by analyzing the structure and performance of the product, the preparation mechanism of high-quality graphene and the importance of regulating and controlling the bubble cleavage process are researched by combining with intermediate product analysis and comparison experiments, and the oxalic acid is innovatively selected as the electrolyte through hundred times of solution selection and experiments, so that the green pollution-free efficient graphene preparation is realized, the expenditure in the aspect of pollution treatment is greatly reduced, the yield is up to more than 95%, and the production cost is greatly reduced.
The technical scheme adopted by the method for solving the problems is as follows: a preparation method of nitrogen-doped single-layer graphene comprises the following steps:
step (1): mixing graphene and melamine according to the mass ratio of 1: 3, fully grinding the mixture by using a grinder, transferring the ground mixture into a quartz furnace, and heating the quartz furnace to 900 ℃ under the protection of nitrogen.
Wherein, the judgment standard for fully grinding the mixture is as follows: the mixture after grinding is in a powder state; the aim of mixing graphene and melamine according to the mass ratio of 1: 3 is to prepare 3.5% nitrogen-doped single-layer graphene.
Step (2): keeping the temperature of the quartz furnace unchanged at 900 ℃, carrying out primary doping for not less than 6 hours, and then cooling the quartz furnace to the normal temperature of 20 ℃, thereby obtaining worm-shaped reactants with the mass equal to M.
And (3): transferring a worm-shaped reactant in a quartz furnace into a reaction kettle, adding oxalic acid deionized water with the mass equal to 10 xM, keeping the temperature of the reaction kettle at 25 ℃, and adding graphene quantum dots with the mass equal to M; wherein the mass fraction of oxalic acid in the oxalic acid deionized water is between 10% and 15%; the diameter of the graphene quantum dot is between 30 nanometers and 40 nanometers.
The method creatively selects oxalic acid as the electrolyte, and can achieve green and pollution-free efficient preparation. In addition, the graphene quantum dots added in the step (3) in the method provided by the invention are selected as the graphene quantum dots with the diameter of 30-40 nanometers, and the size of the graphene quantum dots can be just inserted between layers of graphite, so that better conditions are provided for inserting bubbles, the intercalation of the bubbles is more sufficient, the final yield is greatly improved, and the requirement of industrial production is met.
And (4): keeping the temperature of the reaction kettle at 25 ℃ unchanged, controlling a stirring rod of the reaction kettle to continuously stir for 15 minutes at a rotating speed of 150 revolutions per minute, finishing the first cleavage of the graphite, then heating the reaction kettle to 80 ℃, keeping the temperature of the reaction kettle at 80 ℃ unchanged, continuously controlling the stirring rod of the reaction kettle to continuously stir for 15 minutes at a rotating speed of 150 revolutions per minute, and finishing the second cleavage of the graphite.
It is emphasized that the cleavage occurring stage of the graphite is specifically completed by the step (4), and a double cleavage method is adopted. The reason is that the effect of bubble cleavage at a single temperature is not ideal, and the low-temperature intercalation and high-temperature cleavage are not enough, and researches find that the separate intercalation and stripping steps are particularly important, and in addition, analysis on graphite dynamics shows that the full intercalation can weaken the acting force between graphite layers at a low temperature, and the high temperature is beneficial to the concentrated generation of bubbles, so that the cleavage power is increased. Therefore, the key of the method is to efficiently cleave the graphite structure by taking bubbles as driving materials.
Finally, the single-layer graphene is stripped by oxygen generated by oxalic acid electrolysis, and the oxygen is green and pollution-free gas, so that the environmental pollution is greatly reduced. Meanwhile, oxygen can be locally oxidized in the single-layer graphene, and an oxygen-containing functional group is introduced to serve as a hydrophilic group, so that the water solubility of the graphene can be greatly improved, and the problem of graphene agglomeration can be solved, so that the yield is improved.
And (5): taking out all reaction products in the reaction kettle, filtering by using a filter, transferring the solid product into an ultrasonic machine, and carrying out ultrasonic treatment for 8 hours by using an ethanol solution with volume fraction of 72% as an ultrasonic medium; wherein the ratio of the mass of the solid product to the volume of the ethanol solution is 1: 10; when ultrasonic treatment is carried out, the temperature of the ice-water bath environment inside the ultrasonic machine needs to be controlled not to exceed 35 ℃.
Sonication for up to 8 hours in step (5) above will convert the solid product to a black solution.
And (6): and (3) completely transferring the black solution in the ultrasonic machine into a centrifuge, setting the centrifuge to run for 5 minutes at the rotating speed of 1000 rpm, then collecting the centrifugate, and cleaning the solid residue in the centrifuge.
And (7): centrifuging the collected centrifugate again to obtain a solid residue; the centrifuge process was set to run at 1300 rpm for 10 minutes.
And (8): and taking out the solid residue in the centrifuge, and drying at 50 ℃ to obtain black fluffy powder, wherein the powder is the prepared nitrogen-doped single-layer graphene.
By carrying out the steps described above, the advantages of the method of the invention are presented below.
Firstly, the method can realize pollution-free preparation on the premise of mass production, and the improvement of the performance of the graphene is realized due to the preparation of the nitrogen-doped single-layer graphene, so that some remarkable electrical properties are embodied; secondly, after oxalic acid is used as electrolyte, the method can greatly reduce the difficulty of the subsequent preparation process of the electrochemical bubble stripping preparation mode and improve the efficiency; thirdly, in the preparation method, the graphite can be used for preparing high-quality graphene through intercalation-stripping in a water system, the yield of the high-quality graphene reaches 90.8 percent, which is larger than that of the conventional electrochemical bubble cleavage method, and the whole cleavage process is completed in 40min in the water system, so that the efficiency advantage of chemical bubble cleavage and the characteristics of environmental protection are reflected; fourthly, in the aspect of performance, the high-quality graphene prepared by the method has excellent conductivity (1.01x10S/m), reaches the better level of the high-quality graphene prepared by the intercalation-exfoliation method, and is superior to other methods.
Drawings
FIG. 1 is a schematic flow chart of the method of the present invention.
Detailed Description
The invention is described in detail below with reference to the drawings and the detailed description.
The invention discloses a preparation method of nitrogen-doped single-layer graphene, and the specific implementation mode of the method is described by combining an implementation flow schematic diagram shown in figure 1. The following specific procedures, which are intended to be carried out in small amounts in the laboratory, illustrate the practice and mode of the process of the invention
Step (1): after 10 g of graphene and 30 g of melamine were mixed, the mixture was ground thoroughly using a grinder, the ground mixture was transferred to a quartz furnace, and the quartz furnace was heated to 900 ℃ under nitrogen protection.
Step (2): keeping the temperature of the quartz furnace unchanged at 900 ℃, carrying out primary doping for not less than 6 hours, and then cooling the quartz furnace to the normal temperature of 20 ℃, thereby obtaining a worm-shaped sample.
And (3): transferring the worm-shaped sample in the quartz furnace to a reaction kettle, adding 1000 g of oxalic acid deionized water, keeping the temperature of the reaction kettle at 25 ℃, and adding the graphene quantum dots. The 1000 grams of oxalic acid deionized water contains 100 grams of oxalic acid and 900ml of deionized water, so the mass fraction of oxalic acid deionized water is equal to 10%.
And (4): and controlling the stirring rod of the reaction kettle to continuously stir for 15 minutes according to the rotating speed of 150 revolutions per minute so as to ensure that the intercalation of the bubbles is more sufficient, then heating the reaction kettle to 80 ℃, and continuously controlling the stirring rod of the reaction kettle to continuously stir for 15 minutes according to the rotating speed of 150 revolutions per minute.
And (5): taking out all reaction products in the reaction kettle, filtering the reaction products by a filter, transferring the solid products into an ultrasonic machine, and carrying out ultrasonic treatment on the solid products for 8 hours by using ethanol as an ultrasonic medium; the temperature of the ice-water bath environment inside the ultrasonic machine is controlled not to exceed 35 ℃ in the ultrasonic treatment process.
And (6): and (3) completely transferring the black solution in the ultrasonic machine into a centrifuge, setting the centrifuge to run for 5 minutes at the rotating speed of 1000 rpm, and then collecting the centrifugate.
And (7): centrifuging the collected centrifugate again to obtain a solid sample; the centrifuge process was set to run at 1300 rpm for 10 minutes.
And (8): and taking out a solid sample in the centrifuge, and drying at 50 ℃ to obtain black fluffy powder, wherein the powder is the prepared nitrogen-doped single-layer graphene.
Claims (4)
1. The preparation method of the nitrogen-doped single-layer graphene is characterized by comprising the following steps:
step (1): mixing graphene and melamine according to the mass ratio of 1: 3, fully grinding the mixture by using a grinder, transferring the ground mixture into a quartz furnace, and heating the quartz furnace to 900 ℃ under the protection of nitrogen;
step (2): keeping the temperature of the quartz furnace unchanged at 900 ℃, and cooling the quartz furnace to 20 ℃ after doping for not less than 6 hours, thereby obtaining worm-shaped reactants with the mass equal to M;
and (3): transferring a worm-shaped reactant in a quartz furnace into a reaction kettle, adding oxalic acid deionized water with the mass equal to 10 xM, keeping the temperature of the reaction kettle at 25 ℃, and adding graphene quantum dots with the mass equal to M; wherein the mass fraction of oxalic acid in the oxalic acid deionized water is between 10% and 15%; the diameter of the graphene quantum dot is between 30 and 40 nanometers;
and (4): keeping the temperature of the reaction kettle at 25 ℃ unchanged, controlling a stirring rod of the reaction kettle to perform continuous stirring for 15 minutes at the rotating speed of 150 revolutions per minute, after the first cleavage of the graphite is completed, heating the reaction kettle to 80 ℃, keeping the temperature of the reaction kettle at 80 ℃ unchanged, and continuously controlling the stirring rod of the reaction kettle to perform continuous stirring for 15 minutes at the rotating speed of 150 revolutions per minute to complete the second cleavage of the graphite;
and (5): taking out all reaction products in the reaction kettle, filtering by using a filter, transferring the solid product into an ultrasonic machine, and carrying out ultrasonic treatment for 8 hours by using an ethanol solution with volume fraction of 72% as an ultrasonic medium; wherein the ratio of the mass of the solid product to the volume of the ethanol solution is 1: 10; when ultrasonic treatment is carried out, the temperature of an ice-water bath environment inside the ultrasonic machine needs to be controlled not to exceed 35 ℃;
and (6): transferring all black solution in the ultrasonic machine into a centrifuge, setting the centrifuge to operate for 5 minutes at the rotating speed of 1000 rpm, collecting centrifugal liquid, and cleaning solid residues in the centrifuge;
and (7): centrifuging the collected centrifugate again to obtain a solid residue; in the centrifugal treatment process, the centrifuge is set to run for 10 minutes at the rotating speed of 1300 rpm;
and (8): and taking out the solid residue in the centrifuge, and drying at 50 ℃ to obtain black fluffy powder, wherein the powder is the prepared nitrogen-doped single-layer graphene.
2. The method of claim 1, wherein the criteria for sufficiently grinding the mixture in step (1) with a grinder are: the mixture after grinding is in a powder state; the purpose of mixing graphene and melamine according to the mass ratio of 1: 3 is to prepare 3.5% nitrogen-doped single-layer graphene.
3. The method according to claim 2, wherein the graphene quantum dots with diameters between 30 and 40 nm are selected in the step (4), so as to ensure that the graphene quantum dots are just intercalated between layers of graphite.
4. The method for preparing nitrogen-doped single-layer graphene according to claim 2, wherein the cleavage generation stage of graphite is specifically completed through the step (4), and a double cleavage method is adopted.
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Citations (6)
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| CN102431999A (en) * | 2011-09-22 | 2012-05-02 | 中国科学院金属研究所 | Method for preparing high-quality graphene |
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| CN104058393A (en) * | 2014-06-30 | 2014-09-24 | 上海交通大学 | Method for obtaining sheet layer two-dimensional material by stripping layered three-dimensional material |
| US20150021196A1 (en) * | 2013-07-17 | 2015-01-22 | Aruna Zhamu | Electrochemical method of producing nano graphene platelets |
| CN107879336A (en) * | 2017-11-14 | 2018-04-06 | 郴州国盛新材科技有限公司 | A kind of high electric property graphene nano piece preparation method and its graphene nanometer sheet |
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Patent Citations (6)
| 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 |
| US20150021196A1 (en) * | 2013-07-17 | 2015-01-22 | Aruna Zhamu | Electrochemical method of producing nano graphene platelets |
| CN103910354A (en) * | 2014-03-25 | 2014-07-09 | 复旦大学 | Method for preparing graphene through large-scale aqueous phase |
| CN103935999A (en) * | 2014-05-09 | 2014-07-23 | 中国科学院上海微***与信息技术研究所 | Preparation method of graphene |
| CN104058393A (en) * | 2014-06-30 | 2014-09-24 | 上海交通大学 | Method for obtaining sheet layer two-dimensional material by stripping layered three-dimensional material |
| CN107879336A (en) * | 2017-11-14 | 2018-04-06 | 郴州国盛新材科技有限公司 | A kind of high electric property graphene nano piece preparation method and its graphene nanometer sheet |
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