CN116161642A - Preparation method of N-doped mesoporous carbon aerogel microspheres - Google Patents
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Abstract
The invention discloses a preparation method of N-doped mesoporous carbon aerogel microspheres, which comprises the following steps: adding resorcinol, phloroglucinol, template agent polyethylene glycol 2000 and formaldehyde into pure water, stirring and dissolving to obtain a precursor solution; adding the precursor solution into white oil containing a surfactant, emulsifying, and heating in an oil bath to fully react; centrifugally separating to obtain powder, adding the powder and polyethyleneimine into pure water, and heating in an oil bath for full reaction; centrifugal separation to obtain solid powder, and repeated washing with pure water; and carbonizing to obtain the N-doped carbon aerogel microspheres. According to the invention, polyethyleneimine is used as an N source, and N atom doping modification is carried out on the surface of the carbon aerogel microsphere, so that the electron donating capacity of carbon in a carrier is improved, meanwhile, the cyclic stability in application is obviously improved, and the electrochemical corrosion resistance of the carbon aerogel is improved; the preparation method has the advantages of simple preparation process, short preparation period and low preparation cost, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of porous carbon material preparation, and particularly relates to a preparation method of mesoporous carbon aerogel, which can be used as a platinum-carbon catalyst carrier in proton exchange membrane fuel cell production.
Background
Proton exchange membrane fuel cells have become a research hotspot in the new energy field due to the characteristics of high energy conversion rate, high power density, no pollution and the like. However, pt reserves as catalysts for cathodic redox reactions are limited and expensive, one of the main factors limiting commercial applications of fuel cells. The utilization rate and stability of the Pt can be effectively improved by using a proper carrier to load the Pt, so that the stack cost of the fuel cell is reduced.
The carbon aerogel is used as an amorphous carbon material with adjustable nano three-dimensional network structure, high specific surface area, high porosity and high conductivity, and meets the requirements of platinum-carbon catalyst carriers. The high specific surface area of the carbon aerogel is beneficial to the dispersion of the Pt catalyst on the surface of the carbon aerogel; the high-efficiency three-phase reaction interface can be built by enriching the adjustable pore structure; the high conductivity facilitates electron transfer. At present, the carbon aerogel mainly comprises three forms of carbon aerogel microspheres, carbon aerogel films, blocky carbon aerogel and the like. The preparation of thin films and bulk carbon aerogels generally requires lengthy solvent replacement processes and complex supercritical drying processes, and has long preparation periods, high cost and difficulty in adapting to mass production. The carbon aerogel microsphere is prepared by a microemulsion polymerization method and normal pressure drying, and solvent replacement and supercritical drying processes are not needed, so that the preparation process is relatively simple, the preparation period is shorter, the cost is low, and the carbon aerogel microsphere has the capacity of adapting to mass production. However, the carbon aerogel microspheres have the problems of small pore diameter, difficult adjustment, poor electrochemical corrosion resistance and the like.
The Chinese patent No. 110745807A discloses a carbon aerogel microsphere and a preparation method thereof, which is characterized in that the pore diameter of the carbon aerogel microsphere can be adjusted by controlling the dosage of a pore-forming agent, and the preparation process is simpler and can be suitable for large-scale production. However, many dangling bonds exist on the surface of the carbon aerogel, so that the electrochemical corrosion resistance is not ideal when the carbon aerogel is used as a platinum carbon catalyst carrier. Kou Shuqing et al (national patent publication No. CN 110474060B) disclose a method for preparing a high-efficiency three-dimensional reticular nitrogen self-doping carbon aerogel and application of an oxygen reduction catalyst, which is characterized in that the three-dimensional reticular carbon aerogel can be obtained by utilizing gelatin protein to form nitrogen self-doping without activation treatment. However, the carbon aerogel prepared by the method has smaller pore diameter, which may cause nano Pt to sink into micropores which cannot be accessed by the conductive polymer, so that the nano Pt cannot participate in catalytic reaction, and thus, dead load is caused.
Disclosure of Invention
The invention aims to solve the technical problems that the prior carbon aerogel microsphere has smaller pore diameter and is not resistant to electrochemical corrosion when being used as a platinum-carbon catalyst carrier, and provides a preparation method of the N-doped mesoporous carbon aerogel microsphere, which has the advantages of high mesoporous pore diameter, good electrochemical corrosion resistance, simple preparation process, short preparation period and low preparation cost, and can be suitable for mass production.
In order to achieve the above purpose, the preparation method of the N-doped mesoporous carbon aerogel microspheres is implemented by the following steps:
(1) Precursor solution configuration: adding resorcinol, phloroglucinol and polyethylene glycol 2000 into a certain amount of pure water, heating and stirring until the resorcinol, the phloroglucinol and the polyethylene glycol 2000 are completely dissolved, stopping heating and continuously stirring, cooling to room temperature, adding formaldehyde aqueous solution, and stirring uniformly to prepare precursor solution with the density of 0.2-0.9 g/ml.
(2) Sol-gel reaction: pouring the precursor solution into white oil containing a surfactant, emulsifying by using an emulsifying machine, continuously stirring the emulsified suspension, and simultaneously carrying out water bath reaction to obtain slurry containing gel microspheres;
(3) Solid-liquid separation: the slurry is subjected to solid-liquid separation and repeated washing to obtain gel microspheres;
(4) Doping: adding the gel microspheres into a certain amount of pure water, uniformly mixing by ultrasonic, adding polyethyleneimine, and carrying out water bath reaction to obtain N-doped gel microspheres;
(5) Carbonizing: and carbonizing the doped gel microspheres to obtain the N-doped carbon aerogel microspheres.
As a preferable mode of the preparation method, in the step (1), the molar ratio of resorcinol to phloroglucinol is 1:5-15, and the molar ratio of the sum of resorcinol and phloroglucinol to formaldehyde is 1:1.5-3.
As the preferable preparation method, in the step (1), 2000 amount of polyethylene glycol is added which is 0.1% -5% of the total mass of resorcinol, phloroglucinol and formaldehyde.
As a preferable mode of the preparation method, in the step (2), the surfactant is 0.5-1.5% of the volume of the white oil, and the volume ratio of the precursor solution to the white oil is 1:3-15.
Further, the heating temperature in the step (1) is 20-60 ℃; in the step (2), the stirring speed is 100-500 r/min, the water bath reaction temperature is 30-65 ℃, and the water bath reaction time is 6-15 h.
Further, in the step (4), the mass ratio of the gel microspheres to the pure water is 1:10-300, and the mass ratio of the polyethyleneimine to the gel microspheres is 1:2-15.
Further, in the step (5), the carbonization temperature is 750-1050 ℃, and the carbonization time is 2-6 h.
Experimental study shows that in the step (1), the mol ratio of resorcinol to phloroglucinol is preferably in the range of 1:6-11, and the added polyethylene glycol is preferably 0.5% -2.5% of the total mass of resorcinol, phloroglucinol and formaldehyde.
Researches show that in the step (2), the volume ratio of the precursor solution to the white oil is preferably in the range of 1:5-12; in the step (4), the mass ratio of the gel microspheres to the pure water is preferably 1:80-300, and the mass ratio of the polyethyleneimine to the gel microspheres is preferably 1:5-15.
In order to realize the optimal production efficiency and production cost, the heating temperature in the step (1) is 30-60 ℃; in the step (2), the water bath reaction temperature is 40-60 ℃, and the water bath reaction time is 10-15 h.
Compared with the prior art, the preparation method of the N-doped mesoporous carbon aerogel microsphere has the following beneficial effects:
(1) According to the invention, polyethylene glycol 2000 is used as a template, so that a large amount of mesoporous structures can be generated in the carbon aerogel, and the carbon aerogel can be completely decomposed into gas in a high-temperature carbonization process without secondary removal.
(2) The invention adopts the inverse microemulsion method to synthesize the carbon aerogel microsphere, which is to disperse the precursor solution in each liquid drop wrapped by the oil phase, so that the danger of heat aggregation during large-scale synthesis can be avoided.
(3) According to the invention, the polyethyleneimine is used as an N source, and N atom doping modification is carried out on the surface of the carbon aerogel microsphere, so that the electron donating capacity of carbon in a carrier is improved, meanwhile, the cyclic stability in application is obviously improved, and the electrochemical corrosion resistance of the carbon aerogel is improved.
(4) The preparation method has the advantages of simple preparation process, short preparation period and low preparation cost, and is suitable for large-scale production.
(5) The detection result shows that the particle size of the carbon aerogel microsphere prepared by the method is mainly distributed at 5-15 mu m, the particle size distribution is reasonable, the mesoporous aperture is enlarged by 5-8 times, and the total pore volume is increased by 2.33 times.
(6) When the carbon aerogel microspheres prepared by the method provided by the invention are used as Pt catalyst carriers, the catalytic activity and the cycling stability of the catalyst can be greatly improved. The test result shows that when the Pt content is the same, the initial catalytic activity of the catalyst with the carbon aerogel microsphere as a carrier prepared by the method is 1.84 times that of a commercial platinum carbon catalyst, and after 5000 times of accelerated endurance test, the catalytic activity is 2.3 times that of the commercial platinum carbon catalyst, so that unexpected technical effects are obtained.
Drawings
FIG. 1 is an SEM image of carbon aerogel microspheres prepared according to example 1 of the method of the invention;
FIG. 2 is an EDS diagram of carbon aerogel microspheres prepared according to method example 1 of the present invention;
FIG. 3 is a graph showing pore size distribution of carbon aerogel microspheres prepared in example 1, example 2, and comparative example 1 according to the method of the present invention.
Detailed Description
In order to describe the present invention, the following describes in further detail the preparation method of the N-doped mesoporous carbon aerogel microsphere according to the present invention with reference to examples. The invention is not limited to the examples.
Example 1
The raw materials used for preparing the precursor in the embodiment are as follows: resorcinol, phloroglucinol, formaldehyde, polyethylene glycol 2000, the molar ratio of resorcinol to phloroglucinol is 8:1; the molar ratio of formaldehyde to the total amount of resorcinol and phloroglucinol is 1:1.5; the total mass ratio of the polyethylene glycol 2000 to the resorcinol, the phloroglucinol and the formaldehyde is 0.005:1.
Resorcinol, phloroglucinol and polyethylene glycol 2000 are stirred and dissolved at 60 ℃, and then formaldehyde solution is added to be continuously and uniformly stirred to prepare precursor solution with the density of 0.4 g/ml.
Pouring the precursor solution into 15# white oil containing 0.5% span 80 by volume, emulsifying for 5min at low speed by an emulsifying machine, pouring into a three-neck flask, and reacting for 14h under stirring at 50 ℃ in an oil bath at 100r/min to obtain a suspension; the volume ratio of the precursor to the white oil is 1:5.
The suspension was centrifuged and repeatedly washed with dichloromethane to give a powder free of agglomerations. Adding the powder into an aqueous solution containing 5% of polyethyleneimine by weight of the powder, and reacting in a water bath at 60 ℃ for 10 hours to obtain a turbid solution; wherein the mass ratio of the powder to the pure water is 1:80.
And (3) centrifugally separating the turbid solution, and repeatedly cleaning the turbid solution with pure water to obtain powdery solid.
Carbonizing the powdery solid for 5 hours at 850 ℃ to obtain the N-doped carbon aerogel microspheres.
Example 2
The raw materials used for preparing the precursor in the embodiment are as follows: resorcinol, phloroglucinol, formaldehyde, polyethylene glycol 2000, the molar ratio of resorcinol to phloroglucinol is 9:1; the molar ratio of formaldehyde to the total of resorcinol and phloroglucinol is 1:2; the total mass ratio of the polyethylene glycol 2000 to the resorcinol, the phloroglucinol and the formaldehyde is 0.01:1.
(1) Resorcinol, phloroglucinol and polyethylene glycol 2000 are stirred and dissolved at 50 ℃, and then formaldehyde solution is added to be continuously and uniformly stirred to prepare precursor solution with the density of 0.5 g/ml.
(2) Pouring the precursor solution into 15# white oil containing 1% span 80 by volume, emulsifying for 5min at low speed by an emulsifying machine, pouring into a three-neck flask, and reacting for 14h under stirring at 50 ℃ in an oil bath at 200r/min to obtain a suspension; the volume ratio of the precursor to the white oil is 1:7.
(3) The suspension was centrifuged and repeatedly washed with dichloromethane to give a powder free of agglomerations. Adding the powder into an aqueous solution containing 7% of polyethyleneimine by weight of the powder, and reacting for 12 hours at 60 ℃ in a water bath to obtain a turbid solution; wherein the mass ratio of the powder to the pure water is 1:100.
(4) And (3) centrifugally separating the turbid solution, and repeatedly cleaning the turbid solution with pure water to obtain powdery solid.
(5) Carbonizing the powdery solid for 4 hours at 950 ℃ to obtain the N-doped carbon aerogel microspheres.
Example 3
The raw materials used for preparing the precursor in the embodiment are as follows: resorcinol, phloroglucinol, formaldehyde, polyethylene glycol 2000, the molar ratio of resorcinol to phloroglucinol is 10:1; the molar ratio of formaldehyde to the total of resorcinol and phloroglucinol is 1:2.5; the total mass ratio of the polyethylene glycol 2000 to the resorcinol, the phloroglucinol and the formaldehyde is 0.015:1.
(1) Resorcinol, phloroglucinol and polyethylene glycol 2000 are stirred and dissolved at 40 ℃, and then formaldehyde solution is added to be continuously and uniformly stirred to prepare precursor solution with the density of 0.6 g/ml.
(2) Pouring the precursor solution into 15# white oil containing 1.5% span 80 by volume, emulsifying for 5min at low speed by an emulsifying machine, pouring into a three-neck flask, and reacting for 14h under the conditions of 60 ℃ oil bath and 300r/min stirring to obtain a suspension; the volume ratio of the precursor to the white oil is 1:8.
(3) The suspension was centrifuged and repeatedly washed with dichloromethane to give a powder free of agglomerations. Adding the powder into an aqueous solution containing 10% of polyethyleneimine by weight of the powder, and reacting for 12 hours at 60 ℃ in a water bath to obtain a turbid solution; wherein the mass ratio of the powder to the pure water is 1:150.
(4) And (3) centrifugally separating the turbid solution, and repeatedly cleaning the turbid solution with pure water to obtain powdery solid.
(5) Carbonizing the powdery solid for 4 hours at 1000 ℃ to obtain the N-doped carbon aerogel microspheres.
Example 4
The raw materials used for preparing the precursor in the embodiment are as follows: resorcinol, phloroglucinol, formaldehyde, polyethylene glycol 2000, the molar ratio of resorcinol to phloroglucinol is 11:1; the molar ratio of formaldehyde to the total amount of resorcinol and phloroglucinol is 1:3; the total mass ratio of the polyethylene glycol 2000 to the resorcinol, the phloroglucinol and the formaldehyde is 0.02:1.
(1) Resorcinol, phloroglucinol and polyethylene glycol 2000 are stirred and dissolved at 30 ℃, and then formaldehyde solution is added to be continuously and uniformly stirred to prepare precursor solution with the density of 0.7 g/ml.
(2) Pouring the precursor solution into 15# white oil containing 3% span 80 by volume, emulsifying for 5min at low speed by an emulsifying machine, pouring into a three-neck flask, and reacting for 14h at 60 ℃ in an oil bath to obtain a suspension; the volume ratio of the precursor to the white oil is 1:9.
(3) The suspension was centrifuged and repeatedly washed with dichloromethane to give a powder free of agglomerations. Adding the powder into an aqueous solution containing 10% of polyethyleneimine by weight of the powder, and reacting for 12 hours at 60 ℃ in a water bath to obtain a turbid solution; wherein the mass ratio of the powder to the pure water is 1:200.
(4) And (3) centrifugally separating the turbid solution, and repeatedly cleaning the turbid solution with pure water to obtain powdery solid.
(5) Carbonizing the powdery solid for 4 hours at 1000 ℃ to obtain the N-doped carbon aerogel microspheres.
Example 5
The raw materials used for preparing the precursor in the embodiment are as follows: resorcinol, phloroglucinol, formaldehyde, polyethylene glycol 2000, the molar ratio of resorcinol to phloroglucinol is 15:1; the molar ratio of formaldehyde to the total of resorcinol and phloroglucinol is 1:2.5; the total mass ratio of the polyethylene glycol 2000 to the resorcinol, the phloroglucinol and the formaldehyde is 0.02:1.
(1) Resorcinol, phloroglucinol and polyethylene glycol 2000 are stirred and dissolved at 40 ℃, and then formaldehyde solution is added to be continuously and uniformly stirred to prepare precursor solution with the density of 0.8 g/ml.
(2) Pouring the precursor solution into 15# white oil containing 2% span 80 by volume, emulsifying for 5min at low speed by an emulsifying machine, pouring into a three-neck flask, and reacting for 14h at 60 ℃ in an oil bath to obtain a suspension; the volume ratio of the precursor to the white oil is 1:10.
(3) The suspension was centrifuged and repeatedly washed with dichloromethane to give a powder free of agglomerations. Adding the powder into an aqueous solution containing 30% of polyethyleneimine by weight of the powder, and reacting for 10 hours at 50 ℃ in water bath to prepare a turbid solution; wherein the mass ratio of the powder to the pure water is 1:250.
(4) And (3) centrifugally separating the turbid solution, and repeatedly cleaning the turbid solution with pure water to obtain powdery solid.
(5) Carbonizing the powdery solid for 3 hours at 1050 ℃ to obtain the N-doped carbon aerogel microspheres.
Example 6
The raw materials used for preparing the precursor in the embodiment are as follows: resorcinol, phloroglucinol, formaldehyde, polyethylene glycol 2000, the molar ratio of resorcinol to phloroglucinol is 5:1; the molar ratio of formaldehyde to the total amount of resorcinol and phloroglucinol is 1:3; the total mass ratio of the polyethylene glycol 2000 to the resorcinol, the phloroglucinol and the formaldehyde is 0.02:1.
(1) Resorcinol, phloroglucinol and polyethylene glycol 2000 are stirred and dissolved at 40 ℃, and then formaldehyde solution is added to be continuously and uniformly stirred to prepare precursor solution with the density of 0.8 g/ml.
(2) Pouring the precursor solution into 15# white oil containing 1% span 80 by volume, emulsifying for 5min at low speed by an emulsifying machine, pouring into a three-neck flask, and reacting for 15h at 40 ℃ in an oil bath to obtain a suspension; the volume ratio of the precursor to the white oil is 1:12.
(3) The suspension was centrifuged and repeatedly washed with dichloromethane to give a powder free of agglomerations. Adding the powder into an aqueous solution containing 20% of polyethyleneimine by weight of the powder, and reacting in a water bath at 70 ℃ for 10 hours to obtain a turbid solution; wherein the mass ratio of the powder to the pure water is 1:300.
(4) And (3) centrifugally separating the turbid solution, and repeatedly cleaning the turbid solution with pure water to obtain powdery solid.
(5) Carbonizing the powdery solid for 2 hours at 1050 ℃ to obtain the N-doped carbon aerogel microspheres.
Comparative example 1
The preparation method of the carbon aerogel microsphere of the comparative example is the same, except that the template agent polyethylene glycol 2000 is not added into the precursor solution.
Table 1 carbon aerogel microsphere preparation parameters for various examples
The foregoing description of the preferred embodiment of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
The carbon aerogel microspheres prepared in the example 1 are subjected to electron microscope scanning and energy spectrum spot scanning, and the results are shown in fig. 1 and 2. From the EDS analysis of fig. 1, it can be seen that N was successfully doped to the carbon aerogel microsphere surface. As can be seen from FIG. 2, the prepared carbon aerogel is a microsphere with the particle size mainly distributed in 5-15 mu m, and meanwhile, because the polyethyleneimine is a polymer with amino groups on the main chain, and has both polar groups (amino groups) and nonpolar groups (vinyl groups) in the molecule, the polyethyleneimine long chain can be well loaded on the surface of the carbon aerogel microsphere, so that the surface of the carbon aerogel microsphere has obvious wrinkles.
The carbon aerogel microspheres prepared in example 1, example 2 and comparative example 1 were subjected to pore size test, and the results are shown in fig. 3. It can be seen from fig. 3 that the pore diameters of the carbon aerogel microspheres prepared in the example 1 to which the polyethylene glycol 2000 was not added are mainly concentrated around 3.85nm, the pore diameters of the carbon aerogel microspheres of the example 1 and the example 2 to which the polyethylene glycol 2000 was added are mainly distributed around 20.98 and 31.59, and the mesoporous pore diameters thereof are enlarged 5 to 8 times.
The pore volume, specific surface area, and most probable pore size of the carbon aerogel microspheres prepared by the test examples 1 to 6 and the control example 1 are shown in table 2:
table 2 example carbon aerogel microsphere preparation parameters
As shown in Table 2, the addition of polyethylene glycol not only significantly enlarges the mesoporous pore diameter of the carbon aerogel microsphere, but also greatly improves the total pore volume of the carbon aerogel microsphere, and the total pore volume of the carbon aerogel microsphere prepared in example 2 is improved by 2.33 times compared with that of comparative example 1.
The carbon aerogel microspheres prepared in example 1 and example 2 were Pt-loaded, and cyclic voltammetry was performed under the same conditions with the same Pt content of the commercial platinum carbon catalyst and the electrochemical active area results thereof were calculated as shown in table 3:
table 2 electrochemically active area of example 1, example 2, commercial platinum carbon catalysts
As shown in table 3, the catalyst activity and the cycle stability of the catalyst can be greatly improved when the carbon aerogel microspheres prepared in example 1 and example 2 are used as Pt catalyst carriers after cyclic voltammetry test and accelerated endurance test, the initial catalytic activity of the catalyst with the carbon aerogel microspheres in example 2 as the carriers is 1.84 times that of commercial platinum carbon catalyst when the Pt content is the same, and the catalytic activity after 5000 cycles of accelerated endurance test is 2.3 times that of the commercial platinum carbon catalyst.
Claims (10)
1. The preparation method of the N-doped mesoporous carbon aerogel microsphere is characterized by comprising the following steps of:
(1) Precursor solution configuration: adding resorcinol, phloroglucinol and polyethylene glycol 2000 into a certain amount of pure water, heating and stirring until the resorcinol, the phloroglucinol and the polyethylene glycol 2000 are completely dissolved, stopping heating and continuously stirring, cooling to room temperature, adding formaldehyde aqueous solution, and stirring uniformly to prepare precursor solution with the density of 0.2-0.9 g/ml;
(2) Sol-gel reaction: pouring the precursor solution into white oil containing a surfactant, emulsifying by using an emulsifying machine, continuously stirring the emulsified suspension, and simultaneously carrying out water bath reaction to obtain slurry containing gel microspheres;
(3) Solid-liquid separation: the slurry is subjected to solid-liquid separation and repeated washing to obtain gel microspheres;
(4) Doping: adding the gel microspheres into a certain amount of pure water, uniformly mixing by ultrasonic, adding polyethyleneimine, and carrying out water bath reaction to obtain N-doped gel microspheres;
(5) Carbonizing: and carbonizing the doped gel microspheres to obtain the N-doped carbon aerogel microspheres.
2. The method for preparing the N-doped mesoporous carbon aerogel microspheres according to claim 1, wherein the method comprises the following steps: in the step (1), the mol ratio of resorcinol to phloroglucinol is 1:5-15, and the mol ratio of the sum of resorcinol and phloroglucinol to formaldehyde is 1:1.5-3.
3. The method for preparing the N-doped mesoporous carbon aerogel microspheres according to claim 2, wherein the method comprises the following steps: in the step (1), the added amount of the polyethylene glycol 2000 is 0.1-5% of the total mass of the resorcinol, the phloroglucinol and the formaldehyde.
4. The method for preparing the N-doped mesoporous carbon aerogel microspheres according to claims 1, 2 and 3, wherein the method comprises the following steps: in the step (2), the volume ratio of the precursor solution to the white oil is 1:3-15, wherein the surfactant is 0.5% -1.5% of the volume of the white oil.
5. The method for preparing the N-doped mesoporous carbon aerogel microspheres according to claim 4, wherein the method comprises the following steps: the heating temperature in the step (1) is 20-60 ℃; in the step (2), the stirring speed is 100-500 r/min, the water bath reaction temperature is 30-65 ℃, and the water bath reaction time is 6-15 h.
6. The method for preparing the N-doped mesoporous carbon aerogel microspheres according to claim 5, wherein the method comprises the following steps: in the step (4), the mass ratio of the gel microspheres to the pure water is 1:10-300, and the mass ratio of the polyethyleneimine to the gel microspheres is 1:2-15.
7. The method for preparing the N-doped mesoporous carbon aerogel microspheres according to claim 6, wherein the method comprises the following steps: in the step (5), the carbonization temperature is 750-1050 ℃, and the carbonization time is 2-6 h.
8. The method for preparing the N-doped mesoporous carbon aerogel microspheres according to claim 7, wherein the method comprises the following steps: in the step (1), the mol ratio of resorcinol to phloroglucinol is 1:6-11, and the added amount of polyethylene glycol 2000 is 0.5% -2.5% of the total mass of resorcinol, phloroglucinol and formaldehyde.
9. The method for preparing the N-doped mesoporous carbon aerogel microspheres according to claim 8, wherein the method comprises the following steps: in the step (2), the volume ratio of the precursor solution to the white oil is 1:5-12; in the step (4), the mass ratio of the gel microspheres to the pure water is 1:80-300, and the mass ratio of the polyethyleneimine to the gel microspheres is 1:5-15.
10. The method for preparing the N-doped mesoporous carbon aerogel microspheres according to claim 9, wherein the method comprises the following steps: the heating temperature in the step (1) is 30-60 ℃; in the step (2), the water bath reaction temperature is 40-60 ℃, and the water bath reaction time is 10-15 h.
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