CN114783783B - Preparation method of nitrogen-sulfur co-doped graphene-based composite porous aerogel - Google Patents
Preparation method of nitrogen-sulfur co-doped graphene-based composite porous aerogel Download PDFInfo
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- H—ELECTRICITY
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention provides a preparation method of a nitrogen-sulfur co-doped graphene-based composite porous aerogel material, which comprises the following steps: 1) Preparing polyacrylonitrile porous nano fiber by a thermally induced phase separation method; 2) Preparing graphene oxide grafted polythiophene; 3) Polypyrrolidone is used as a surfactant, and ZIF-8 is prepared by an alcohol heating method; 4) Preparing carbon fiber/nitrogen-sulfur co-doped graphene/porous carbon composite porous aerogel; the preparation method has the characteristics of stable process, easy operation, reliable quality, low cost, light weight, no pollution and the like, and has good commercialization prospect.
Description
Technical Field
The invention relates to a preparation method of nitrogen-sulfur co-doped graphene-based composite porous aerogel, belonging to the field of composite materials and electrochemistry.
Background
The graphene aerogel is high-strength oxidized aerogel, has the characteristics of high elasticity and strong adsorption, and is widely applied to the fields of communication, adsorption materials, sensors, quenching, electrodes and the like. The current preparation method of the high-strength graphene oxide aerogel mainly comprises the following steps of firstly dispersing graphene oxide in deionized water to prepare a dispersion liquid with the concentration of 0.1-10 mg/mL; and adding the dispersion liquid into a hydrothermal reaction kettle to react for about 10 hours at the temperature of 100-200 ℃ to obtain graphene oxide hydrogel, and finally, putting the graphene oxide hydrogel into ammonia water to soak for 24 hours, and freeze-drying to obtain the high-strength aerogel. The graphene oxide aerogel has large specific surface area, high porosity and good conductivity, so that the graphene oxide aerogel is widely applied to electrode materials of super capacitors. However, graphene is easy to be stacked in the use process, and the specific capacitance and the energy density of the graphene are greatly influenced. In order to further improve the specific capacitance of graphene oxide, the graphene oxide aerogel is often subjected to mixed modification. For example, song Huimin and other people use p-benzoquinone as a redox active agent, a hydrothermal method is used for preparing polypyrrole/graphene hydrogel, and the redox active composite aerogel prepared after freeze drying is beneficial to obtaining an ordered three-dimensional network structure after the p-benzoquinone is introduced. When the concentration of the p-benzoquinone is 5mmol/L, the composite aerogel can obtain the optimal electrochemical performance, the specific capacitance can reach 304.0F/g, and 79.88% of the initial specific capacitance can be maintained after 10000 times of circulation. The active carbon and the active carbon are assembled into an asymmetric super capacitor, and high energy density (41.56 Wh/kg) and power density (400W/kg) can be obtained.
The invention comprises the following steps:
the invention aims to provide a preparation method of a nitrogen-sulfur co-doped graphene-based composite porous aerogel material, which aims to solve the problems in the prior art.
In order to achieve the above object, the technical scheme of the present invention is as follows:
a preparation method of nitrogen-sulfur co-doped graphene-based composite porous aerogel comprises the following steps:
preparing polyacrylonitrile porous nanofiber by using a thermally induced phase separation method;
adding zinc nitrate and 2-methylimidazole into a methanol solvent, adding polyvinylpyrrolidone, stirring for reaction, standing, centrifuging, drying, heating the product from 25 ℃ to 300-350 ℃ at a speed of 5-10 ℃/min under the protection of nitrogen, keeping the temperature for 3-5 hours, and naturally cooling to obtain a ZIF-8 metal organic framework;
preparing graphene oxide grafted polythiazole;
dispersing the polyacrylonitrile porous nanofiber and graphene oxide grafted polythiazole in deionized water, adding a ZIF-8 metal organic framework, and continuously performing ultrasonic dispersion and stirring to obtain a polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 dispersion;
pouring the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 dispersion liquid into a mold, and sequentially performing liquid nitrogen freezing treatment and freeze drying to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 aerogel;
heating the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 aerogel to 250-300 ℃ from 25 ℃ under the protection of nitrogen, preserving heat for 2-3 h, then heating to 900-1000 ℃ from 250-300 ℃ and preserving heat for 10-15 h to obtain the carbon fiber/nitrogen-sulfur co-doped graphene/porous carbon composite porous aerogel, namely the nitrogen-sulfur co-doped graphene composite porous aerogel material.
As a preferred scheme, the preparation method of the polyacrylonitrile porous nanofiber comprises the following steps:
dissolving polyacrylonitrile in dimethyl sulfoxide, and then adding tetraethyl orthosilicate and glacial acetic acid to obtain a precursor solution;
freezing the precursor solution at the temperature of minus 40 to minus 10 ℃ for 100 to 200 minutes, removing the solvent, and freeze-drying to obtain the polyacrylonitrile/silicon dioxide composite nanofiber;
and soaking the polyacrylonitrile/silicon dioxide composite nanofiber in hydrofluoric acid, washing and drying to obtain the polyacrylonitrile porous nanofiber.
Preferably, in the precursor solution, the mass concentration of polyacrylonitrile is 4-8%, and the mass concentration of tetraethyl orthosilicate is 0.4-1%.
As a preferable scheme, the mass ratio of the zinc nitrate to the 2-methylimidazole is (2-4): (5-15).
As a preferable scheme, the preparation method of the graphene oxide grafted polythiazole comprises the following steps:
adding concentrated sulfuric acid into crystalline flake graphite and phosphoric acid, then adding potassium permanganate, reacting for 2 hours, heating to 50 ℃ for continuous reaction for 1 hour, cooling to room temperature, adding ice water, stirring, dropwise adding hydrogen peroxide, carrying out suction filtration, washing and vacuum drying to obtain graphene oxide;
dispersing the graphene oxide in concentrated ammonia water, performing hydrothermal reaction at 95 ℃, and performing suction filtration, washing with distilled water and vacuum drying to obtain amino modified graphene oxide;
and uniformly mixing the amino modified graphene oxide, isopropanol, distilled water, a hydrochloric acid solution and thiazole, dropwise adding an ammonium persulfate aqueous solution under the condition of ice-water bath, and reacting for 6 hours to obtain graphene oxide grafted polythiazole.
As a preferable scheme, the mass ratio of the crystalline flake graphite to the phosphoric acid is (1-4): (5-12); the mass ratio of the amino modified graphene oxide to the thiazole is (1-3): (3-6).
As a preferable scheme, the mass ratio of the polyacrylonitrile porous nanofiber to the graphene oxide grafted polythiazole to the ZIF-8 metal organic framework is (2-3): (1-2): (4-6).
A composite porous aerogel material obtained by the aforementioned preparation method.
The basic principle of the invention is as follows:
1) Polyacrylonitrile is used as a polymer, tetraethyl orthosilicate is used as a precursor, and the polyacrylonitrile/silicon dioxide composite nanofiber is obtained through a thermally induced phase separation method, freeze drying and solvent removal. Immersing the composite nanofiber in hydrofluoric acid, and removing silicon dioxide to obtain the polyacrylonitrile porous nanofiber.
2) Taking polypyrrolidone as a surfactant, reacting zinc nitrate with 2-dimethylimidazole by adopting an alcohol heating method, and finally calcining to obtain ZIF-8;
3) Preparing graphene oxide by adopting an improved Hummer method, reacting amino groups on the graphene oxide under the condition of heating and pressurizing, and grafting and copolymerizing thiazole on the graphene oxide by taking the amino groups on the graphene oxide as active points to obtain graphene oxide grafted polythiazole.
4) And dispersing the polyacrylonitrile porous nanofiber, graphene oxide grafted polythiazole and ZIF-8 in deionized water, and then freezing with liquid nitrogen and freeze-drying to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 aerogel. Finally, pre-oxidizing and carbonizing the aerogel at a high temperature, converting the polyacrylonitrile porous nanofiber into carbon fiber, converting graphene oxide grafted polythiazole into nitrogen-sulfur co-doped graphene, and finally obtaining the carbon fiber/nitrogen-sulfur co-doped graphene/porous carbon composite porous aerogel.
Compared with the prior art, the invention has the following beneficial effects:
1) The three-dimensional carbon network skeleton prevents the stacking of the nitrogen-sulfur co-doped graphene, improves the contact area between the nitrogen-sulfur co-doped graphene and the electrolyte, and greatly improves the specific capacitance of the aerogel material.
2) The carbon fiber/nitrogen-sulfur co-doped graphene/porous carbon composite porous aerogel electrode material utilizes a ZIF-8 fluffy three-dimensional framework structure, so that the transfer of electrolyte ions is promoted, and the wettability between the electrolyte and the electrode is improved.
3) The preparation method has the characteristics of stable process, easy operation, reliable quality, low cost, light weight, no pollution and the like, and has good commercialization prospect.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is a scanning electron microscope image of the nitrogen-sulfur co-doped graphene-based composite porous aerogel prepared by the method.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Example 1
The embodiment relates to a preparation method of composite porous aerogel, the preparation route is shown in fig. 1, and the preparation method specifically comprises the following steps:
1) Preparation of polyacrylonitrile porous nanofiber
Dissolving 1.0g of polyacrylonitrile in 20g of dimethyl sulfoxide solvent, stirring and dissolving at 50 ℃ to obtain a polyacrylonitrile solution, and adding 0.1g of tetraethyl orthosilicate and 0.5g of glacial acetic acid into the polyacrylonitrile solution to obtain a precursor solution; freezing the precursor solution at-20deg.C for 120min, adding into distilled water to remove dimethyl sulfoxide solvent, and freeze drying to obtain polyacrylonitrile/silicon dioxide composite nanofiber. Soaking the composite nanofiber in 1mol/L hydrofluoric acid, oscillating for 24 hours in a constant-temperature water bath, washing and drying to obtain the polyacrylonitrile porous nanofiber.
2) Preparation of ZIF-8
0.3g of zinc nitrate and 1.0g of 2-methylimidazole are weighed and added into 50mL of methanol solvent, magnetic stirring is carried out for dissolution, then 0.05g of polyvinylpyrrolidone is added, stirring reaction is carried out at 60 ℃ for 6 hours, then standing is carried out for 24 hours, a white turbid solution is formed, precipitate obtained by centrifugation is washed 5 times with methanol, and drying is carried out in an oven at 80 ℃ for 8 hours. And (3) putting the dried product into a muffle furnace, heating the dried product from 25 ℃ to 320 ℃ at a speed of 7 ℃/min under the protection of nitrogen, keeping the temperature for 5 hours, and naturally cooling to obtain the ZIF-8.
3) Preparation of graphene oxide grafted polythiazole
1.25g of crystalline flake graphite and 4g of phosphoric acid are added into a three-necked flask, the three-necked flask is placed into an ice-water bath, 20mL of concentrated sulfuric acid is slowly added, magnetic stirring is carried out for 10min, 2.2g of potassium permanganate is slowly added, and the reaction is carried out for 2h. And (3) heating to 50 ℃ to continue the reaction for 1h, cooling to room temperature, adding 100mL of ice water into the reaction liquid, stirring, dropwise adding 1mL of hydrogen peroxide (the mass concentration is 30%), filtering, washing and vacuum drying to obtain the graphene oxide.
Adding 0.3g of graphene oxide into a 30mL pressure reaction kettle, then adding strong ammonia water, reacting for 6 hours at 95 ℃, cooling, filtering, washing with distilled water, and drying in vacuum to obtain the amino modified graphene oxide. To a three-necked flask, 0.2g of amino-modified graphene oxide, 2mL of isopropanol, 15mL of distilled water, 40mL of 2mol/mL of hydrochloric acid solution and 0.6g of thiazole were added, the three-necked flask was placed in an ice-water bath, and after that, 10g of an aqueous ammonium persulfate solution with a mass concentration of 10% was slowly added, and the reaction was stirred for 6 hours. And (5) carrying out suction filtration, washing and vacuum drying to obtain graphene oxide grafted polythiazole.
4) Preparation of nitrogen-sulfur co-doped graphene-based composite porous aerogel material
Dispersing 0.06g of polyacrylonitrile porous nanofiber and 0.03g of graphene oxide grafted polythiazole in 200mL of deionized water, performing ultrasonic dispersion for 30min, adding 0.15g of ZIF-8 into the dispersion after ultrasonic dispersion, and performing continuous ultrasonic dispersion and stirring to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 dispersion. And pouring the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 dispersion liquid into a mold, freezing in liquid nitrogen at the temperature of minus 196 ℃ for 20min, and drying in a freeze dryer for 24h after the completion of the freezing treatment to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 aerogel. And (3) placing the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 aerogel in a tube furnace, heating to 280 ℃ from 25 ℃ under the protection of nitrogen, preserving heat for 2h, then heating to 950 ℃ from 280 ℃ and preserving heat for 13h, and finally obtaining the carbon fiber/nitrogen-sulfur co-doped graphene/porous carbon composite porous aerogel, namely the nitrogen-sulfur co-doped graphene-based composite porous aerogel material.
The morphology of the nitrogen-sulfur co-doped graphene-based composite porous aerogel prepared in the embodiment 1 is shown in fig. 1, and a scanning electron microscope shows that the aerogel is of a three-dimensional porous structure. The porosity of the electrode material is 96.4%, and the specific surface area is 501m 2 And/g. The specific capacitance of the electrode material is 350F/g under the condition of the current density of 1A/g.
Example 2
1) Preparation of polyacrylonitrile porous nanofiber
Dissolving 1.1g of polyacrylonitrile in 20g of dimethyl sulfoxide solvent, stirring and dissolving at 50 ℃ to obtain a polyacrylonitrile solution, and adding 0.15g of tetraethyl orthosilicate and 0.5g of glacial acetic acid into the polyacrylonitrile solution to obtain a precursor solution; freezing the precursor solution at-30deg.C for 150min, adding into distilled water to remove dimethyl sulfoxide solvent, and freeze drying to obtain polyacrylonitrile/silicon dioxide composite nanofiber. Soaking the composite nanofiber in 1mol/L hydrofluoric acid, oscillating for 24 hours in a constant-temperature water bath, washing and drying to obtain the polyacrylonitrile porous nanofiber.
2) Preparation of ZIF-8
0.35g of zinc nitrate and 1.2g of 2-methylimidazole are weighed and added into 50mL of methanol solvent, magnetic stirring is carried out for dissolution, then 0.05g of polyvinylpyrrolidone is added, stirring reaction is carried out at 60 ℃ for 6 hours, then standing is carried out for 24 hours, a white turbid solution is formed, precipitate obtained by centrifugation is washed 5 times with methanol, and drying is carried out in an oven at 80 ℃ for 8 hours. And (3) putting the dried product into a muffle furnace, heating the dried product from 25 ℃ to 330 ℃ at a speed of 8 ℃/min under the protection of nitrogen, keeping the temperature for 4 hours, and naturally cooling to obtain the ZIF-8.
3) Preparation of graphene oxide grafted polythiazole
1.1g of crystalline flake graphite and 3.7g of phosphoric acid are added into a three-necked flask, the three-necked flask is placed into an ice-water bath, 20mL of concentrated sulfuric acid is slowly added, magnetic stirring is carried out for 10min, 3g of potassium permanganate is slowly added, and the reaction is carried out for 2h. And (3) heating to 50 ℃ to continue the reaction for 1h, cooling to room temperature, adding 100mL of ice water into the reaction liquid, stirring, dropwise adding 1mL of hydrogen peroxide (the mass concentration is 30%), filtering, washing and vacuum drying to obtain the graphene oxide.
Adding 0.3g of graphene oxide into a 30mL pressure reaction kettle, then adding strong ammonia water, reacting for 6 hours at 95 ℃, cooling, filtering, washing with distilled water, and drying in vacuum to obtain the amino modified graphene oxide. To a three-necked flask, 0.3g of amino-modified graphene oxide, 2mL of isopropanol, 15mL of distilled water, 40mL of 2mol/mL of hydrochloric acid solution and 0.4g of thiazole were added, the three-necked flask was placed in an ice-water bath, and after that, 10g of an aqueous ammonium persulfate solution with a mass concentration of 10% was slowly added, and the reaction was stirred for 6 hours. And (5) carrying out suction filtration, washing and vacuum drying to obtain graphene oxide grafted polythiazole.
4) Preparation of nitrogen-sulfur co-doped graphene-based composite porous aerogel material
Dispersing 0.05g of polyacrylonitrile porous nanofiber and 0.025 g of graphene oxide grafted polythiazole in 200mL of deionized water, performing ultrasonic dispersion for 30min, adding 0.1g of ZIF-8 into the dispersion after ultrasonic dispersion, and performing continuous ultrasonic dispersion and stirring to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 dispersion. And pouring the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 dispersion liquid into a mold, freezing in liquid nitrogen at the temperature of minus 196 ℃ for 20min, and drying in a freeze dryer for 24h after the completion of the freezing treatment to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 aerogel. And (3) placing the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 aerogel in a tube furnace, heating to 300 ℃ from 25 ℃ under the protection of nitrogen, preserving heat for 3h, then heating to 950 ℃ from 300 ℃ and preserving heat for 12h, and finally obtaining the carbon fiber/nitrogen-sulfur co-doped graphene/porous carbon composite porous aerogel, namely the nitrogen-sulfur co-doped graphene-based composite porous aerogel material.
The nitrogen-sulfur co-doped graphene-based composite porous aerogel electrode material prepared in example 2 has a porosity of 93.1% and a specific surface area of 498m 2 And/g. The specific capacitance of the electrode material is 312F/g under the condition of the current density of 1A/g.
Example 3
1) Preparation of polyacrylonitrile porous nanofiber
Dissolving 1.2g of polyacrylonitrile in 20g of dimethyl sulfoxide solvent, stirring and dissolving at 50 ℃ to obtain a polyacrylonitrile solution, and adding 0.12g of tetraethyl orthosilicate and 0.5g of glacial acetic acid into the polyacrylonitrile solution to obtain a precursor solution; freezing the precursor solution at-15 ℃ for 130min, then putting the precursor solution into distilled water to remove dimethyl sulfoxide solvent, and freeze-drying to obtain the polyacrylonitrile/silicon dioxide composite nanofiber. Soaking the composite nanofiber in 1mol/L hydrofluoric acid, oscillating for 24 hours in a constant-temperature water bath, washing and drying to obtain the polyacrylonitrile porous nanofiber.
2) Preparation of ZIF-8
0.4g of zinc nitrate and 1.1g of 2-methylimidazole are weighed and added into 50mL of methanol solvent, magnetic stirring is carried out for dissolution, then 0.05g of polyvinylpyrrolidone is added, stirring reaction is carried out at 60 ℃ for 6 hours, then standing is carried out for 24 hours, a white turbid solution is formed, precipitate obtained by centrifugation is washed 5 times with methanol, and drying is carried out in an oven at 80 ℃ for 8 hours. And (3) putting the dried product into a muffle furnace, heating the dried product from 25 ℃ to 300 ℃ at a speed of 6 ℃/min under the protection of nitrogen, keeping the temperature for 5 hours, and naturally cooling to obtain the ZIF-8.
3) Preparation of graphene oxide grafted polythiazole
1.2g of crystalline flake graphite and 5g of phosphoric acid are added into a three-necked flask, the three-necked flask is placed into an ice-water bath, 20mL of concentrated sulfuric acid is slowly added, magnetic stirring is carried out for 10min, 1.8g of potassium permanganate is slowly added, and the reaction is carried out for 2h. And (3) heating to 50 ℃ to continue the reaction for 1h, cooling to room temperature, adding 100mL of ice water into the reaction liquid, stirring, dropwise adding 1mL of hydrogen peroxide (the mass concentration is 30%), filtering, washing and vacuum drying to obtain the graphene oxide.
Adding 0.3g of graphene oxide into a 30mL pressure reaction kettle, then adding strong ammonia water, reacting for 6 hours at 95 ℃, cooling, filtering, washing with distilled water, and drying in vacuum to obtain the amino modified graphene oxide. To a three-necked flask, 0.3g of amino-modified graphene oxide, 2mL of isopropanol, 15mL of distilled water, 40mL of 2mol/mL of hydrochloric acid solution and 0.5g of thiazole were added, the three-necked flask was placed in an ice-water bath, and after that, 10g of an aqueous ammonium persulfate solution with a mass concentration of 10% was slowly added, and the reaction was stirred for 6 hours. And (5) carrying out suction filtration, washing and vacuum drying to obtain graphene oxide grafted polythiazole.
4) Preparation of nitrogen-sulfur co-doped graphene-based composite porous aerogel material
Dispersing 0.03g of polyacrylonitrile porous nanofiber and 0.02 g of graphene oxide grafted polythiazole in 200mL of deionized water, performing ultrasonic dispersion for 30min, adding 0.1g of ZIF-8 into the dispersion after ultrasonic dispersion, and performing continuous ultrasonic dispersion and stirring to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 dispersion. And pouring the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 dispersion liquid into a mold, freezing in liquid nitrogen at the temperature of minus 196 ℃ for 20min, and drying in a freeze dryer for 24h after the completion of the freezing treatment to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 aerogel. And (3) placing the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 aerogel in a tube furnace, heating to 290 ℃ from 25 ℃ under the protection of nitrogen, preserving heat for 2h, then heating to 960 ℃ from 290 ℃ and preserving heat for 11h, and finally obtaining the carbon fiber/nitrogen-sulfur co-doped graphene/porous carbon composite porous aerogel, namely the nitrogen-sulfur co-doped graphene-based composite porous aerogel material.
The nitrogen-sulfur co-doped graphene-based composite porous aerogel electrode material prepared in example 3 has a porosity of 95.2% and a specific surface area of 482m 2 And/g. The specific capacitance of the electrode material is 333F/g under the condition of the current density of 1A/g.
Comparative example 1
Different from example 1, in the step 1), the addition amount of tetraethyl orthosilicate is 0, and finally the carbon fiber/nitrogen-sulfur co-doped graphene composite porous aerogel is obtained. The porosity of the aerogel electrode material is 90.1 percent, and the specific surface area is 408m 2 And/g. The specific capacitance of the electrode material is 280F/g under the condition of the current density of 1A/g.
Comparative example 2
Unlike example 1, in step 4), the "graphene oxide grafted polythiazole" was replaced with "graphene oxide" to finally obtain the carbon fiber/graphene oxide/ZIF-8 composite porous aerogel. The porosity of the aerogel electrode material is 95.1 percent, and the specific surface area is 511m 2 And/g. The specific capacitance of the electrode material is 271F/g under the condition of the current density of 1A/g.
Comparative example 3
Unlike example 1, in step 4), the "polyacrylonitrile porous nanofiber" was replaced with a commercially available "polyacrylonitrile powder" to finally obtain the carbon/nitrogen-sulfur co-doped graphene oxide/ZIF-8 composite porous aerogel. The porosity of the aerogel electrode material is 88.1 percent, and the specific surface area is 310m 2 And/g. The specific capacitance of the electrode material is 261F/g under the condition of the current density of 1A/g.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.
Claims (6)
1. The preparation method of the nitrogen-sulfur co-doped graphene-based composite porous aerogel is characterized by comprising the following steps of:
preparing polyacrylonitrile porous nanofiber by using a thermally induced phase separation method;
adding zinc nitrate and 2-methylimidazole into a methanol solvent, adding polyvinylpyrrolidone, stirring for reaction, standing, centrifuging, drying, heating the product from 25 ℃ to 300-350 ℃ at a speed of 5-10 ℃/min under the protection of nitrogen, keeping the temperature for 3-5 hours, and naturally cooling to obtain a ZIF-8 metal organic framework;
preparing graphene oxide grafted polythiazole;
dispersing the polyacrylonitrile porous nanofiber and graphene oxide grafted polythiazole in deionized water, adding a ZIF-8 metal organic framework, and continuously performing ultrasonic dispersion and stirring to obtain a polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 dispersion;
pouring the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 dispersion liquid into a mold, and sequentially performing liquid nitrogen freezing treatment and freeze drying to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 aerogel;
heating the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 aerogel to 250-300 ℃ from 25 ℃ under the protection of nitrogen, preserving heat for 2-3 hours, then heating to 900-1000 ℃ from 250-300 ℃ and preserving heat for 10-15 hours to obtain carbon fiber/nitrogen-sulfur co-doped graphene/porous carbon composite porous aerogel, namely the nitrogen-sulfur co-doped graphene composite porous aerogel material;
the preparation method of the polyacrylonitrile porous nanofiber comprises the following steps:
dissolving polyacrylonitrile in dimethyl sulfoxide, and then adding tetraethyl orthosilicate and glacial acetic acid to obtain a precursor solution;
freezing the precursor solution at the temperature of minus 40 to minus 10 ℃ for 100 to 200 minutes, removing the solvent, and freeze-drying to obtain the polyacrylonitrile/silicon dioxide composite nanofiber;
soaking the polyacrylonitrile/silicon dioxide composite nanofiber in hydrofluoric acid, washing and drying to obtain a polyacrylonitrile porous nanofiber;
the preparation method of the graphene oxide grafted polythiazole comprises the following steps:
adding concentrated sulfuric acid into crystalline flake graphite and phosphoric acid, then adding potassium permanganate, reacting 2h, heating to 50 ℃, continuing to react 1h, cooling to room temperature, adding ice water, stirring, dropwise adding hydrogen peroxide, carrying out suction filtration, washing, and carrying out vacuum drying to obtain graphene oxide;
dispersing the graphene oxide in concentrated ammonia water, performing hydrothermal reaction at 95 ℃, and performing suction filtration, washing with distilled water and vacuum drying to obtain amino modified graphene oxide;
and uniformly mixing the amino modified graphene oxide, isopropanol, distilled water, a hydrochloric acid solution and thiazole, dropwise adding an ammonium persulfate aqueous solution under the condition of ice-water bath, and reacting 6h to obtain the graphene oxide grafted polythiazole.
2. The method for preparing the nitrogen-sulfur co-doped graphene-based composite porous aerogel according to claim 1, wherein the mass concentration of polyacrylonitrile in the precursor solution is 4-8%, and the mass concentration of tetraethyl orthosilicate is 0.4-1%.
3. The preparation method of the nitrogen-sulfur co-doped graphene-based composite porous aerogel according to claim 1, wherein the mass ratio of zinc nitrate to 2-methylimidazole is (2-4): (5-15).
4. The method for preparing the nitrogen-sulfur co-doped graphene-based composite porous aerogel according to claim 1, wherein the mass ratio of the crystalline flake graphite to the phosphoric acid is (1-4): (5-12); the mass ratio of the amino modified graphene oxide to the thiazole is (1-3): (3-6).
5. The preparation method of the nitrogen-sulfur co-doped graphene-based composite porous aerogel according to claim 1, wherein the mass ratio of the polyacrylonitrile porous nanofiber to the graphene oxide grafted polythiazole to the ZIF-8 metal organic framework is (2-3): (1-2): (4-6).
6. A composite porous aerogel material obtained by the production method according to any one of claims 1 to 5.
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