CN111137872A - Large-scale production method of nitrogen-rich doped amorphous carbon/graphitic carbon nanocomposite powder - Google Patents
Large-scale production method of nitrogen-rich doped amorphous carbon/graphitic carbon nanocomposite powder Download PDFInfo
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Abstract
A large-scale production method of nitrogen-rich doped amorphous carbon/graphitic carbon nano composite powder belongs to the technical field of nano powder production. The method is characterized in that pyrrole, ammonium persulfate, concentrated hydrochloric acid, graphite carbon and other raw materials widely used in industry are utilized, a simple wet chemical in-situ polymerization method and a common heat treatment method are combined to polymerize and carbonize a conductive high polymer material polypyrrole, so that the nitrogen doping amount of the amorphous carbon/graphite carbon composite nano powder is increased, and the nitrogen-enriched doped amorphous carbon/graphite carbon composite nano powder with different length-diameter ratios is formed by controlling the proportion of pyrrole monomers to graphite carbon. The invention greatly improves the production efficiency, reduces the cost, realizes the large-scale production of the amorphous carbon/graphite carbon composite nano powder with different nitrogen doping amounts, simultaneously avoids the pollution in the powder preparation process by utilizing a wet chemical method and a multi-time cleaning technology, and improves the purity of the powder.
Description
Technical Field
The invention belongs to the technical field of nano powder production, and relates to a large-scale production method of a nitrogen-rich doped amorphous carbon/graphitic carbon nano composite.
Background
While the wet chemical process is a process for preparing materials by chemical reaction with participation of a liquid phase, the heat treatment process is one of the most common processes in industrial production. The combination of wet chemical methods and subsequent thermal treatment processes is commonly used in the preparation of amorphous carbon materials. However, for preparing amorphous carbon material doped with heterogeneous elements (such as nitrogen, N), and simultaneously maintaining proper nanostructure, and being used for large-scale industrial production, there are many technical problems, mainly manifested in how to prepare heterogeneous atom doped amorphous carbon with special structure and its composite with graphitic carbon in large scale and maintain higher doping content of heterogeneous atoms with high efficiency, low cost, high purity and no pollution.
The existing wet chemistry and heat treatment combined process for preparing heterogeneous atom doped amorphous carbon and graphite carbon composite material has the following main points:
(1) low production efficiency and high cost
At present, in order to make the heterogeneous atom doped amorphous carbon/graphitic carbon composite material have suitable porosity, other surfactants or other solvent molecules except water are often required to be added, such as polyoxyethylene polyoxypropylene ether block copolymer (F127), polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), sodium dodecylbenzene sulfonate, imidazole ionic liquid and the like, and the substances added can be indeed used as substances dissolved in solvent water, so that a suitable pore structure is created in the subsequent heat treatment, but the production cost is also increased. In addition, in order to dissolve these substances, the actual dissolution time accounts for 20-80% of the total production time, and overall, the production efficiency is low. Meanwhile, in order to dissolve the substances, a large amount of energy is consumed by processing methods such as ultrasonic treatment and the like, so that the production cost is increased; the difficulty of removing these materials during subsequent cleaning processes will further increase the production costs.
(2) The purity is lower
After other surfactants or other solvent molecules except water are added, the substances and production materials are easy to interact, such as hydrogen bonds, covalent bonds, van der waals force and the like, so that the substances are extremely difficult to remove in the subsequent cleaning process, and the purification of the amorphous carbon doped with the hetero atoms and the composite nano powder thereof is more difficult.
(3) Cannot realize the real large-scale production
The existing production process for preparing the heterogeneous atom doped amorphous carbon and the composite thereof is limited by the problems of more carbon source selection, less raw materials required by composite production, complex and low-efficiency production process, higher equipment cost required by material preparation, longer production time, difficulty in removing other impurities easily introduced by a wet chemical method and the like, increases the production cost, reduces the production efficiency, and cannot realize the large-scale and high-quality production of the heterogeneous atom doped amorphous carbon and the composite thereof in a real sense.
Disclosure of Invention
The invention aims to solve the technical problems of low hetero atom doping content of amorphous carbon, difficult large-scale preparation on the premise of ensuring high nitrogen element doping content, low preparation purity and the like.
In order to achieve the purpose, the invention provides the following technical scheme:
a large-scale production method of nitrogen-rich doped amorphous carbon/graphitic carbon nanocomposite powder comprises the following steps: (1) selecting raw materials: graphite carbon (including multi-walled carbon nanotubes or graphene oxide), pyrrole monomers, water, ammonium persulfate and concentrated hydrochloric acid are selected as raw materials for large-scale production of wet chemistry nitrogen-rich doped amorphous carbon/graphite carbon composite powder, the raw materials are common raw materials in industry, and the selection is favorable for reducing the production cost of the powder.
The purity of the multi-wall carbon nano tube is more than or equal to 95 percent, and the diameter and the length of the multi-wall carbon nano tube are adjustable; the purity of the graphene oxide is more than or equal to 95%, and the number of stacked graphite sheets is adjustable; the purity of the pyrrole monomer is more than or equal to 99 percent, and the water content is less than 0.1 percent; the purity of the ammonium persulfate is more than or equal to 95 percent; the concentration of concentrated hydrochloric acid was 12 mol/L.
(2) And (3) pyrrole purification treatment: distilling the purchased industrial pyrrole monomer under reduced pressure, continuously introducing nitrogen for protection in the process, preventing the pyrrole monomer from being oxidized, heating the pyrrole liquid to 90-100 ℃ by using an oil bath after the reduced pressure, and sealing and shading after distillation, and putting the pyrrole liquid in a refrigerator for cooling and storage;
in the oil bath, glycerol (glycerin) is used.
(3) Pretreatment of graphite carbon: (a) putting an industrial-grade multi-walled carbon nanotube into a mixed solution containing concentrated sulfuric acid and concentrated nitric acid, heating the multi-walled carbon nanotube in an oil bath within a certain temperature range under the condition that the temperature is continuously increased for 1.5-2.5 hours, condensing, refluxing and continuously stirring the high-temperature solution in the process, wherein the step is suitable for large-scale acidification modification of the original multi-walled carbon nanotube, and the modified acidified carbon nanotube (CNTs-COOH) has more active chemical property and is easier to carry out composite reaction with other reactants; and (b) the industrial-grade graphene oxide does not need pretreatment.
The final temperature range of the temperature rise of the oil bath heating is 130-160 ℃, and the temperature rise speed is 0.5-1/min. In the mixed solution, the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 4: 1; the mass fraction of the concentrated sulfuric acid is more than or equal to 70 percent, and the mass fraction of the concentrated nitric acid is about 68 percent.
(4) Graphite carbon dispersion: and dissolving the acidified multi-walled carbon nano-tube or graphene oxide in water, and ultrasonically dispersing for more than or equal to 1 hour until a turbid liquid or a solution is formed. The acidified multi-walled carbon nanotubes still cannot be dissolved in water, and a uniform suspension is finally formed; graphene oxide can be dissolved in water to form a homogeneous solution.
The mass ratio of the carbon nano tube or the graphene oxide to the water can be controllably adjusted according to the specific requirements of a producer, wherein the mass fraction of the carbon material is not higher than 0.02% (relative to the total mass of the carbon material and the water).
(5) And (3) pyrrole dispersion: and (3) dropwise adding the pyrrole monomer purified in the step (1) into the suspension or solution in the step (4) under the condition of normal-temperature rapid stirring, and stirring for at least 1 hour to form uniform suspension or solution.
The stirring speed is more than or equal to 500 r/min, the mass ratio of the purified pyrrole monomer to the water is controllably adjusted according to the specific requirements of a producer, wherein the mass fraction of the pyrrole is not higher than 0.2 percent (relative to the total mass of the pyrrole and the water).
(6) Controlling the environment of the reaction solution: adding concentrated hydrochloric acid into the suspension/solution of (5).
The volume ratio of the concentrated hydrochloric acid to water is controllably adjusted according to the specific requirements of producers, wherein the molar fraction range of the concentrated hydrochloric acid is 0.5-2 mol/L.
(7) Pyrrole in-situ polymerization: adding ammonium persulfate into the suspension/solution in the step (6), and continuously stirring for 24 hours under the condition of an ice water bath, wherein the reaction temperature is controlled to be 0-5 ℃;
the mole number of the ammonium persulfate is controlled to be consistent with that of the added pyrrole, and the stirring speed is more than or equal to 500 r/min.
(8) Cleaning and collecting the nitrogen-rich doped amorphous carbon/graphite carbon nano composite powder: and (3) carrying out vacuum filtration and cleaning on the reaction solution in the step (7), wherein cleaning solvents are water and absolute ethyl alcohol, the cleaning frequency of each solvent is not less than three times, finally drying at 60 ℃ for at least 12 hours, and collecting the powder, namely the nitrogen-enriched doped amorphous carbon/graphite carbon nano composite powder (PPy-CNTs), wherein the micropores in the powder are fewer, and a porous structure meeting the requirement is formed by subsequent heat treatment.
The stirring and cleaning time of the water and the absolute ethyl alcohol is respectively 5-8 hours and 1-2 hours, and the stirring speed is 400-600 revolutions per minute.
(9) And (3) at room temperature, placing the powder dried and collected in the step (8) in an environment filled with nitrogen, raising the temperature in the environment at a certain raising rate until the final temperature is 400-1000 ℃, then preserving the temperature for 2 hours, then naturally cooling, in the process, introducing pure nitrogen and isolating air until the reaction temperature is reduced to room temperature, and finally collecting the prepared powder, thus obtaining the nitrogen-enriched doped amorphous carbon/graphite carbon nano composite powder product (N-C @ CNTs).
And (3) the temperature rising speed in the step (9) is 1-10 ℃/min.
Compared with the prior art, the invention has the beneficial effects that:
1) is beneficial to large-scale production and cost reduction
From the aspect of raw material selection, the raw materials selected by the production process are all raw materials which are commonly used in industry and have lower cost, and the nitrogen-rich doped amorphous carbon/carbon nanotube nano composite powder is produced on a large scale by the raw materials which have low price and are convenient for large-scale production, and simultaneously, the properties of the prepared material, such as porous property, ultrahigh nitrogen content, formation of one-dimensional/two-dimensional nano structure and the like, are ensured; from the subsequent wet chemistry and heat treatment processes, the process steps are simple, the operation is simple and convenient, the cost of required production equipment is low, the energy consumption is low, the process is suitable for large-scale production, and the production cost is controlled.
2) Realize high-efficiency production
In the invention, all production processes except raw material pretreatment are innovatively integrated in two production environments, namely room temperature, low temperature solution and high temperature nitrogen atmosphere, so that the problem of unavoidable environmental conversion in the production process of the amorphous carbon and the amorphous carbon nano-tube nano-composite powder is avoided to the greatest extent, and the high-efficiency production of the amorphous carbon/carbon nano-tube nano-composite powder is realized.
3) Achieving high content nitrogen doping of amorphous carbon materials
The method is characterized in that the content of doped foreign atoms of the amorphous carbon material is very difficult to improve, for a graphite carbon source, a stable carbon atom ring of the carbon source means that the foreign atoms are difficult to combine with a carbon ring of the carbon source in a covalent bond, a hydrogen bond and other modes, for a non-graphite carbon source, the foreign element doping is guaranteed to be carried out in two modes, namely external doping and internal retention.
4) Realizing nanostructure construction of amorphous carbon material
The method for constructing the nano structure of the amorphous carbon material is extremely difficult for most amorphous carbon materials, and most amorphous carbon materials can be realized only by extremely complicated and harsh experimental conditions.
5) Amorphous carbon/carbon nano tube nano composite powder purity improvement
The method avoids adding other surfactants or other solvent molecules except water, reduces the difficulty degree of the subsequent cleaning process, and ensures that the purity of the heterogeneous atom doped amorphous carbon and the composite nano powder thereof can reach 99.9 percent.
Drawings
FIG. 1 is an X-ray diffraction pattern of a nitrogen-enriched doped amorphous carbon/graphitic carbon nanocomposite prepared in example 1.
Figure 2 is a SEM photograph of the nitrogen-enriched doped amorphous carbon/graphitic carbon nanocomposite prepared in example 1.
Figure 3 is a TEM micrograph of the nitrogen-enriched doped amorphous carbon/graphitic carbon nanocomposite prepared in example 1.
FIG. 4 is a photograph of a BET of nitrogen-doped amorphous carbon/graphitic carbon nanocomposite prepared in example 1 (Brunauer-Emmett-Teller, obtained by nitrogen adsorption testing).
FIG. 5 is a drawing of an abstract, illustrating the process of preparing nitrogen-rich doped amorphous carbon/graphitic carbon nanocomposites.
Detailed Description
The following detailed description of the embodiments of the invention refers to the accompanying drawings.
Example 1
1. Distilling pyrrole monomer (10ml, purity more than or equal to 99% and water content less than 0.1%) under reduced pressure, introducing nitrogen for protection, heating to 90 deg.C with oil bath (glycerol ) after reduced pressure, distilling, sealing and shading, and storing in refrigerator;
2. putting a multi-walled carbon nanotube (2g, the purity is more than or equal to 95%) into a mixed solution containing concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 4:1, the total volume is 40ml, the mass fraction of the concentrated sulfuric acid is more than or equal to 70%, and the mass fraction of the concentrated nitric acid is 68%), heating the mixed solution in an oil bath for 2.5 hours under the condition of continuously increasing the temperature within a certain temperature range, and condensing, refluxing and continuously stirring the high-temperature solution in the process (the final temperature of the temperature increase of the oil bath heating is 130 ℃, the temperature increase speed is 0.5 ℃/min, and the stirring speed of the continuous stirring is 500 r/min);
3. adding 40mg of acidified CNTs/industrial graphene oxide (the purity is more than or equal to 95%) into 200ml of deionized water, and carrying out ultrasonic treatment for 1h with the ultrasonic power of 60W to form suspension/solution containing the acidified CNTs/industrial graphene oxide;
4. stirring the suspension/solution for 30min under the condition of ice water bath, wherein the stirring speed is 500 revolutions per minute;
5. dripping 0.4ml of pyrrole into the constant pressure funnel, and stirring for 30min at the stirring speed of 500 r/min;
6. 8.3ml of concentrated hydrochloric acid (the concentration is 12mol/L) is dropped in, 1.36g of ammonium persulfate is added, and the mixture is continuously stirred in an ice-water bath, the reaction temperature is 0 ℃, and the stirring speed is 400 r/min;
7. stirring for 24 hours, then washing with deionized water and absolute ethyl alcohol for three times (stirring time is 5 and 1 hours in the cleaning process, and rotating speed is 600 revolutions per minute) respectively, and finally drying at 60 ℃ for 12 hours to finally obtain two powder samples;
8. placing the two kinds of dried and collected powder in an environment filled with nitrogen, raising the temperature in the environment at a heating rate of 1 ℃ (the initial temperature is room temperature) until the temperature is 400 ℃, preserving the temperature for 2 hours, then naturally cooling, introducing pure nitrogen and isolating air in the process until the reaction temperature is reduced to the room temperature, and finally collecting the prepared powder, thereby obtaining the nitrogen-rich doped amorphous carbon/graphite carbon nano composite powder product. As shown in the attached figure 1 of the specification, a characteristic peak at 25.9 degrees 2 theta corresponds to a (002) crystal face of the composite; FIGS. 2 and 3 show a carbon nanotube and a one-dimensional structure thereof; figure 4 illustrates that the composite is a typical type I pore structure (micropores predominate).
Example 2
1. Distilling pyrrole monomer (10ml, purity more than or equal to 99% and water content less than 0.1%) under reduced pressure, introducing nitrogen for protection, heating to 100 deg.C with oil bath (glycerol ) after reduced pressure, distilling, sealing and shading, and storing in refrigerator;
2. putting a multi-walled carbon nanotube (2g, the purity is more than or equal to 95%) into a mixed solution containing concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 4:1, and the total volume is 40ml, wherein the mass fraction of the concentrated sulfuric acid is more than or equal to 70%, and the mass fraction of the concentrated nitric acid is 68%), heating the mixed solution in an oil bath for 1.5 hours under the condition of continuously increasing the temperature within a certain temperature range, and condensing, refluxing and continuously stirring the high-temperature solution in the process (the final temperature of the temperature increase of the oil bath heating is 160 ℃, the temperature increase speed is 1 ℃/min, and the stirring speed of the continuous stirring is 500 r/min);
3. adding 20mg of acidified CNTs/industrial graphene oxide (the purity is more than or equal to 95%) into 200ml of deionized water, and carrying out ultrasonic treatment for 1h with the ultrasonic power of 60W to form suspension/solution containing the acidified CNTs/industrial graphene oxide;
4. stirring the suspension/solution for 30min under the condition of ice water bath, wherein the stirring speed is 500 revolutions per minute;
5. dripping 0.25ml of pyrrole into a constant pressure funnel, and stirring for 30min at the stirring speed of 500 r/min;
6. 33.2ml of concentrated hydrochloric acid (the concentration is 12mol/L) is dropped in, 0.85g of ammonium persulfate is added, and the mixture is continuously stirred in an ice-water bath, the reaction temperature is 5 ℃, and the stirring speed is 500 r/min;
7. stirring for 24 hours, then washing with deionized water and absolute ethyl alcohol for three times (stirring time is 8 and 2 hours in the cleaning process, and rotating speed is 400 revolutions per minute) respectively at a stirring speed of 600 revolutions per minute, and finally drying at 60 ℃ for 12 hours to finally obtain two powder samples;
8. placing the two kinds of dried and collected powder in an environment filled with nitrogen, raising the temperature in the environment at a heating rate of 10 ℃ (the initial temperature is room temperature) until the temperature is 1000 ℃, preserving the temperature for 2 hours, then naturally cooling, introducing pure nitrogen and isolating air in the process until the reaction temperature is reduced to the room temperature, and finally collecting the prepared powder, thereby obtaining the nitrogen-rich doped amorphous carbon/graphite carbon nano composite powder product.
Example 3
1. Distilling pyrrole monomer (10ml, purity more than or equal to 99% and water content less than 0.1%) under reduced pressure, introducing nitrogen for protection, heating to 95 deg.C with oil bath (glycerol ) after reduced pressure, distilling, sealing and shading, and storing in refrigerator;
2. putting a multi-walled carbon nanotube (2g, the purity is more than or equal to 95%) into a mixed solution containing concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 4:1, and the total volume is 40ml, wherein the mass fraction of the concentrated sulfuric acid is more than or equal to 70%, and the mass fraction of the concentrated nitric acid is 68%), heating the mixed solution in an oil bath for 2 hours under the condition of continuously increasing the temperature within a certain temperature range, and condensing, refluxing and continuously stirring the high-temperature solution in the process (the final temperature of the temperature increase of the oil bath heating is 140 ℃, the temperature increase speed is 0.8 ℃/min, and the stirring speed of the continuous stirring is 500 r/min);
3. adding 10mg of acidified CNTs/industrial graphene oxide (the purity is more than or equal to 95%) into 200ml of deionized water, and carrying out ultrasonic treatment for 1h with the ultrasonic power of 60W to form suspension/solution containing the acidified CNTs/industrial graphene oxide;
4. stirring the suspension/solution for 30min under the condition of ice water bath, wherein the stirring speed is 500 revolutions per minute;
5. dripping 0.2ml of pyrrole into a constant pressure funnel, and stirring for 30min at the stirring speed of 500 r/min;
6. 16.6ml of concentrated hydrochloric acid (the concentration is 12mol/L) is dropped in, 0.68g of ammonium persulfate is added, and the mixture is continuously stirred in an ice-water bath, the reaction temperature is 0 ℃, and the stirring speed is 500 r/min;
7. stirring for 24 hours, then washing with deionized water and absolute ethyl alcohol for three times (stirring time is 6 and 1.5 hours in the cleaning process, and rotating speed is 500 revolutions per minute) respectively, and finally drying for 12 hours at 60 ℃ to finally obtain two powder samples;
8. placing the two kinds of dried and collected powder in an environment filled with nitrogen, raising the temperature in the environment at a temperature raising rate of 5 ℃ (the initial temperature is room temperature) until 600 ℃, preserving the temperature for 2 hours, then naturally cooling, introducing pure nitrogen and isolating air in the process until the reaction temperature is reduced to room temperature, and finally collecting the prepared powder, thereby obtaining the nitrogen-rich doped amorphous carbon/graphite carbon nano composite powder product.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.
Claims (5)
1. A large-scale production method of nitrogen-rich doped amorphous carbon/graphitic carbon nanocomposite powder is characterized by comprising the following steps:
(1) selecting raw materials: selecting graphite carbon, pyrrole monomer, water, ammonium persulfate and concentrated hydrochloric acid as raw materials for large-scale production of wet chemical nitrogen-rich doped amorphous carbon/graphite carbon composite powder; wherein the graphitic carbon comprises multi-walled carbon nanotubes or graphene oxide;
(2) and (3) pyrrole purification treatment: carrying out reduced pressure distillation on the pyrrole monomer, introducing nitrogen for protection in the process, heating to 90-100 ℃ by using an oil bath after reducing the pressure, sealing and shading, and placing in a refrigerator for cooling and storing;
(3) pretreatment of graphite carbon: (a) putting the multi-walled carbon nano-tube into a mixed solution of concentrated sulfuric acid and concentrated nitric acid for pretreatment, wherein the pretreatment temperature is 130-160 ℃, and the pretreatment time is 1.5-2.5 hours; (b) the graphene oxide does not need to be pretreated;
(4) graphite carbon dispersion: dissolving the multi-walled carbon nanotubes or graphene oxide pretreated in the step (3) in water, and performing ultrasonic dispersion until a suspension or a solution is formed: the pretreated multi-walled carbon nano-tube can not be dissolved in water to form uniform turbid liquid; the graphene oxide can be dissolved in water to form a uniform solution; the mass ratio of the pure carbon nano tube or the graphene oxide to the water is adjustable, wherein the mass fraction of the carbon material is not higher than 0.02%;
(5) and (3) pyrrole dispersion: dropwise adding the pyrrole monomer purified in the step (1) into the suspension or solution in the step (4) under the condition of normal-temperature rapid stirring, and stirring for at least 1 hour to form uniform suspension or solution; the mass ratio of the purified pyrrole monomer to the water is adjustable, wherein the mass fraction of the pyrrole is not higher than 0.2 percent
(6) Controlling the environment of the reaction solution: adding concentrated hydrochloric acid into the suspension/solution in the step (5); the volume ratio of the concentrated hydrochloric acid to water is adjustable, wherein the molar fraction of the concentrated hydrochloric acid is in the range of 0.5-2 mol/L;
(7) pyrrole in-situ polymerization: adding ammonium persulfate into the suspension/solution in the step (6), and continuously stirring for 24 hours under the condition of an ice-water bath; the mole number of the ammonium persulfate is the same as that of the added pyrrole;
(8) cleaning and collecting the nitrogen-rich doped amorphous carbon/graphite carbon nano composite powder: vacuum pumping, filtering and washing the reaction solution in the step (7), and drying at 60 ℃;
(9) and (3) at room temperature, placing the powder dried and collected in the step (8) in an environment filled with nitrogen, preserving the temperature for 2 hours when the temperature reaches 400-1000 ℃, then naturally cooling to room temperature, and introducing pure nitrogen and isolating air all the time in the process to obtain the product.
2. The method for mass production of nitrogen-enriched doped amorphous carbon/graphitic carbon nanocomposite powder according to claim 1, wherein the purity of the multi-walled carbon nanotube in step (1) is not less than 95%, and the diameter and length thereof are adjustable; the purity of the graphene oxide is more than or equal to 95%, and the number of stacked graphite sheets is adjustable; the purity of the pyrrole monomer is more than or equal to 99 percent, and the water content is less than 0.1 percent; the purity of the ammonium persulfate is more than or equal to 95 percent; the concentration of concentrated hydrochloric acid was 12 mol/L.
3. The method for mass production of nitrogen-enriched doped amorphous carbon/graphitic carbon nanocomposite powder according to claim 1, wherein in the mixed solution of step (3), the volume ratio of concentrated sulfuric acid to concentrated nitric acid is 4: 1; the mass fraction of the concentrated sulfuric acid is more than or equal to 70 percent, and the mass fraction of the concentrated nitric acid is about 68 percent.
4. The method for mass production of nitrogen-enriched doped amorphous carbon/graphitic carbon nanocomposite powder according to claim 1, wherein the reaction temperature in step (6) is controlled to be 0-5 ℃.
5. The method for mass production of nitrogen-enriched doped amorphous carbon/graphitic carbon nanocomposite powder according to claim 1, wherein in the cleaning process in the step (7), the cleaning solvent is water and absolute ethyl alcohol, and the stirring and cleaning time of water and absolute ethyl alcohol is 5-8 hours and 1-2 hours respectively.
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Application publication date: 20200512 |