CN114783783A - Preparation method of nitrogen and sulfur co-doped graphene-based composite porous aerogel - Google Patents
Preparation method of nitrogen and sulfur co-doped graphene-based composite porous aerogel Download PDFInfo
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Abstract
The invention provides a preparation method of a nitrogen and sulfur co-doped graphene-based composite porous aerogel material, which comprises the following steps: 1) preparing polyacrylonitrile porous nanofiber by a thermally induced phase separation method; 2) preparing graphene oxide grafted polythiophene; 3) taking polyvinylpyrrolidone as a surfactant, and preparing ZIF-8 by an alcohol heating method; 4) preparing carbon fiber/nitrogen and sulfur co-doped graphene/porous carbon composite porous aerogel; the preparation method has the characteristics of stable process, easiness in operation, reliable quality, low cost, light weight, no pollution and the like, and has good commercial prospect.
Description
Technical Field
The invention relates to a preparation method of a nitrogen and sulfur co-doped graphene-based composite porous aerogel, belonging to the field of composite materials and electrochemistry.
Background
The graphene aerogel is a high-strength oxide 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 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 for reaction at the temperature of 100 ℃ and 200 ℃ for about 10 hours to obtain graphene oxide hydrogel, finally putting the graphene oxide hydrogel into ammonia water, soaking for 24 hours, and freeze-drying to obtain the high-strength aerogel. Due to the large specific surface area, the high porosity and the good conductivity of the graphene oxide aerogel, the graphene oxide aerogel is widely applied to electrode materials of super capacitors. However, graphene is easy to stack in the using process, and the specific capacitance and energy density of graphene are greatly influenced. In order to further improve the specific capacitance of the graphene oxide, the graphene oxide aerogel is often subjected to mixed modification. For example, songhem et al use p-benzoquinone as a redox active agent, a hydrothermal method is used for preparing polypyrrole/graphene hydrogel, and the polypyrrole/graphene hydrogel is freeze-dried to obtain the redox active composite aerogel which is favorable for obtaining an ordered three-dimensional network structure after being introduced into the p-benzoquinone. When the concentration of the p-benzoquinone is 5mmol/L, the composite aerogel can obtain the best electrochemical performance, the specific capacitance can reach 304.0F/g, and 79.88% of the initial specific capacitance can be kept after circulation for 10000 times. The composite material and active carbon are assembled into an asymmetric super capacitor, and high energy density (41.56Wh/kg) and power density (400W/kg) can be obtained.
The invention content is as follows:
the invention aims to provide a preparation method of a nitrogen and sulfur co-doped graphene-based composite porous aerogel material, which aims to solve the problems in the prior art.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a nitrogen and 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, then adding polyvinylpyrrolidone, stirring for reaction, standing, centrifuging, drying, heating the product from 25 ℃ to 300-350 ℃ at the speed of 5-10 ℃/min under the protection of nitrogen, keeping the temperature for 3-5 h, and naturally cooling to obtain a ZIF-8 metal organic frame;
preparing graphene oxide grafted polythiazole;
dispersing the polyacrylonitrile porous nanofiber and the 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 solution;
pouring the polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 dispersion liquid into a mold, and sequentially carrying out liquid nitrogen freezing treatment and freeze drying to obtain polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 aerogel;
the method comprises the steps of heating polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 aerogel from 25 ℃ to 250-300 ℃ under the protection of nitrogen, preserving heat for 2-3 hours, heating from 250-300 ℃ to 900-1000 ℃, and preserving heat for 10-15 hours to obtain carbon fiber/nitrogen and sulfur co-doped graphene/porous carbon composite porous aerogel, namely the nitrogen and sulfur co-doped graphene-based 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-40 to-10 ℃ for 100 to 200min, removing the solvent, and freeze-drying to obtain 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%.
Preferably, the mass ratio of the zinc nitrate to the 2-methylimidazole is (2-4): (5-15).
As a preferred 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 ℃, continuing to react for 1 hour, cooling to room temperature, adding ice water, stirring, dropwise adding hydrogen peroxide, performing suction filtration, washing and vacuum drying to obtain graphene oxide;
dispersing the graphene oxide in strong ammonia water, carrying out hydrothermal reaction at 95 ℃, carrying out suction filtration, washing with distilled water, and vacuum drying to obtain amino modified graphene oxide;
and (3) 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 an ice water bath, and reacting for 6 hours to obtain the graphene oxide grafted benzothiazole.
Preferably, 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).
According to 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 preparation method.
The basic principle of the invention is as follows:
1) polyacrylonitrile is taken as a polymer, tetraethoxysilane is taken as a precursor, and the polyacrylonitrile/silicon dioxide composite nanofiber is obtained by a thermally induced phase separation method, freeze drying and solvent removal. And (3) soaking the composite nanofiber in hydrofluoric acid to remove silicon dioxide to obtain the polyacrylonitrile porous nanofiber.
2) Taking polyvinylpyrrolidone as a surfactant, reacting zinc nitrate with 2-dimethyl imidazole by an alcohol heating method, and finally calcining to obtain ZIF-8;
3) preparing graphene oxide by adopting an improved Hummer method, reacting amino on the graphene oxide under the conditions of heating and pressurizing, and grafting and copolymerizing thiazole on the graphene oxide by using the amino on the graphene oxide as an active point to obtain the graphene oxide grafted polythiazole.
4) And (3) dispersing the polyacrylonitrile porous nanofiber, the graphene oxide grafted polythiazole and the ZIF-8 in deionized water, and then freezing by using liquid nitrogen and freeze-drying to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 aerogel. And finally, pre-oxidizing the aerogel and carbonizing the aerogel at high temperature, converting polyacrylonitrile porous nano fibers into carbon fibers, converting oxidized graphene grafted polythiazole into nitrogen and sulfur co-doped graphene, and finally obtaining the carbon fiber/nitrogen and sulfur co-doped graphene/porous carbon composite porous aerogel.
Compared with the prior art, the invention has the following beneficial effects:
1) the existence of three-dimensional carbon network skeleton has prevented piling up of nitrogen sulphur codope graphite alkene, has improved the area of contact between nitrogen sulphur codope graphite alkene and the electrolyte, improves aerogel material's specific capacitance greatly.
2) The carbon fiber/nitrogen and sulfur co-doped graphene/porous carbon composite porous aerogel electrode material has the advantages that the ZIF-8 fluffy three-dimensional skeleton structure is utilized, the transfer of electrolyte ions is promoted, and the wettability between electrolyte and an electrode is improved.
3) The preparation method has the characteristics of stable process, easiness in operation, reliable quality, low cost, light weight, no pollution and the like, and has good commercial prospect.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
fig. 1 is a scanning electron microscope image of the nitrogen and sulfur co-doped graphene-based composite porous aerogel prepared by the invention.
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 invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
Example 1
The embodiment relates to a preparation method of a composite porous aerogel, wherein 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; and (3) freezing the precursor solution at-20 ℃ for 120min, then putting the precursor solution into distilled water to remove the dimethyl sulfoxide solvent, and freeze-drying to obtain the polyacrylonitrile/silicon dioxide composite nanofiber. And (3) soaking the composite nanofiber in 1mol/L hydrofluoric acid, oscillating in a constant-temperature water bath for 24 hours, washing and drying to obtain the polyacrylonitrile porous nanofiber.
2) Preparation of ZIF-8
Weighing 0.3g of zinc nitrate and 1.0g of 2-methylimidazole, adding the zinc nitrate and the 2-methylimidazole into 50mL of methanol solvent, magnetically stirring for dissolving, then adding 0.05g of polyvinylpyrrolidone, stirring for reacting for 6 hours at 60 ℃, standing for 24 hours to form a white turbid solution, washing the precipitate obtained by centrifugation with methanol for 5 times, and drying 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 the speed of 7 ℃/min under the protection of nitrogen, keeping the temperature for 5 hours, and naturally cooling to obtain ZIF-8.
3) Preparation of graphene oxide grafted polythiazole
Adding 1.25g of crystalline flake graphite and 4g of phosphoric acid into a three-neck flask, placing the three-neck flask into an ice-water bath, slowly adding 20mL of concentrated sulfuric acid, magnetically stirring for 10min, slowly adding 2.2g of potassium permanganate, and reacting for 2 h. And heating to 50 ℃, continuing to react for 1h, cooling to room temperature, adding 100mL of ice water into the reaction solution, stirring, dropwise adding 1mL of hydrogen peroxide (with the mass concentration of 30%), performing suction filtration, washing and vacuum drying to obtain the graphene oxide.
And adding 0.3g of graphene oxide into a 30mL pressure reaction kettle, then adding concentrated ammonia water, reacting for 6 hours at 95 ℃, cooling, performing suction filtration, washing with distilled water, and performing vacuum drying to obtain the amino modified graphene oxide. 0.2g of amino modified graphene oxide, 2mL of isopropanol, 15mL of distilled water, 40mL of 2mol/mL hydrochloric acid solution and 0.6g of thiazole are added into a three-neck flask, the three-neck flask is placed in an ice-water bath, 10g of 10% ammonium persulfate aqueous solution is slowly added, and the mixture is stirred and reacted for 6 hours. And carrying out suction filtration, washing and vacuum drying to obtain the graphene oxide grafted polythiazole.
4) Preparation of nitrogen and sulfur co-doped graphene-based composite porous aerogel material
And (3) 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 liquid after the ultrasonic treatment is finished, and performing continuous ultrasonic dispersion and stirring to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted polythiazole/ZIF-8 dispersion liquid. Pouring the polyacrylonitrile porous nanofiber/graphene oxide grafted benzothiazole/ZIF-8 dispersion liquid into a mold, freezing in liquid nitrogen at the temperature of-196 ℃ for 20min, and drying in a freeze dryer for 24h after the freezing is finished to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 aerogel. Placing polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 aerogel in a tubular furnace, heating from 25 ℃ to 280 ℃ under the protection of nitrogen, preserving heat for 2 hours, then heating from 280 ℃ to 950 ℃, and preserving heat for 13 hours to finally obtain the carbon fiber/nitrogen and sulfur co-doped graphene/porous carbon composite porous aerogel, namely the nitrogen and sulfur co-doped graphene-based composite porous aerogel material.
The appearance of the nitrogen and sulfur co-doped graphene-based composite porous aerogel prepared in example 1 is shown in fig. 1, and a scanning electron microscope shows that the aerogel has a three-dimensional porous structure. The porosity of the electrode material is 96.4%, and the specific surface area is 501m2(iv) g. The specific capacitance of the electrode material is 350F/g under the condition that the current density is 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-30 ℃ for 150min, then putting the precursor solution into distilled water to remove the dimethyl sulfoxide solvent, and freeze-drying to obtain the polyacrylonitrile/silicon dioxide composite nanofiber. And (3) soaking the composite nanofiber in 1mol/L hydrofluoric acid, oscillating in a constant-temperature water bath for 24h, washing and drying to obtain the polyacrylonitrile porous nanofiber.
2) Preparation of ZIF-8
Weighing 0.35g of zinc nitrate and 1.2g of 2-methylimidazole, adding the zinc nitrate and the 2-methylimidazole into 50mL of methanol solvent, magnetically stirring for dissolving, then adding 0.05g of polyvinylpyrrolidone, stirring for reacting for 6 hours at 60 ℃, standing for 24 hours to form a white turbid solution, washing the precipitate obtained by centrifugation with methanol for 5 times, and drying in an oven at 80 ℃ for 8 hours. And (3) putting the dried product into a muffle furnace, heating from 25 ℃ to 330 ℃ at a speed of 8 ℃/min under the protection of nitrogen, keeping the temperature for 4h, and naturally cooling to obtain ZIF-8.
3) Preparation of graphene oxide grafted polythiazole
Adding 1.1g of crystalline flake graphite and 3.7g of phosphoric acid into a three-neck flask, placing the three-neck flask into an ice-water bath, slowly adding 20mL of concentrated sulfuric acid, magnetically stirring for 10min, slowly adding 3g of potassium permanganate, and reacting for 2 h. And heating to 50 ℃, continuing to react for 1h, cooling to room temperature, adding 100mL of ice water into the reaction solution, stirring, dropwise adding 1mL of hydrogen peroxide (with the mass concentration of 30%), performing suction filtration, washing and vacuum drying to obtain the graphene oxide.
And adding 0.3g of graphene oxide into a 30mL pressure reaction kettle, then adding concentrated ammonia water, reacting for 6 hours at 95 ℃, cooling, performing suction filtration, washing with distilled water, and performing vacuum drying to obtain the amino modified graphene oxide. 0.3g of amino modified graphene oxide, 2mL of isopropanol, 15mL of distilled water, 40mL of 2mol/mL hydrochloric acid solution and 0.4g of thiazole are added into a three-neck flask, the three-neck flask is placed in an ice-water bath, 10g of 10% ammonium persulfate aqueous solution is slowly added, and the mixture is stirred and reacted for 6 hours. And (4) carrying out suction filtration, washing and vacuum drying to obtain the graphene oxide grafted polythiazole.
4) Preparation of nitrogen and sulfur co-doped graphene-based composite porous aerogel material
And (3) dispersing 0.05g of polyacrylonitrile porous nanofiber and 0.025 g of graphene oxide grafted benzothiazole in 200mL of deionized water, performing ultrasonic dispersion for 30min, adding 0.1g of ZIF-8 into the dispersion liquid after the ultrasonic treatment is finished, and performing continuous ultrasonic dispersion and stirring to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 dispersion liquid. Pouring the polyacrylonitrile porous nanofiber/graphene oxide grafted benzothiazole/ZIF-8 dispersion liquid into a mold, freezing in liquid nitrogen at the temperature of-196 ℃ for 20min, and drying in a freeze dryer for 24h after the freezing is finished to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 aerogel. Placing polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 aerogel in a tubular furnace, heating from 25 ℃ to 300 ℃ under the protection of nitrogen, preserving heat for 3 hours, then heating from 300 ℃ to 950 ℃, preserving heat for 12 hours, and finally obtaining the carbon fiber/nitrogen and sulfur co-doped graphene/porous carbon composite porous aerogel, namely the nitrogen and sulfur co-doped graphene-based composite porous aerogel material.
The nitrogen and 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 498m2(ii) in terms of/g. The specific capacitance of the electrode material is 312F/g under the condition that the current density is 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; and (3) freezing the precursor solution at-15 ℃ for 130min, then putting the precursor solution into distilled water to remove the dimethyl sulfoxide solvent, and carrying out freeze drying to obtain the polyacrylonitrile/silicon dioxide composite nanofiber. And (3) soaking the composite nanofiber in 1mol/L hydrofluoric acid, oscillating in a constant-temperature water bath for 24 hours, washing and drying to obtain the polyacrylonitrile porous nanofiber.
2) Preparation of ZIF-8
Weighing 0.4g of zinc nitrate and 1.1g of 2-methylimidazole, adding the zinc nitrate and the 2-methylimidazole into 50mL of methanol solvent, magnetically stirring for dissolving, then adding 0.05g of polyvinylpyrrolidone, stirring for reacting for 6 hours at 60 ℃, standing for 24 hours to form a white turbid solution, washing the precipitate obtained by centrifugation with methanol for 5 times, and drying in an oven at 80 ℃ for 8 hours. And (3) putting the dried product into a muffle furnace, heating from 25 ℃ to 300 ℃ at the speed of 6 ℃/min under the protection of nitrogen, keeping the temperature for 5 hours, and naturally cooling to obtain ZIF-8.
3) Preparation of graphene oxide grafted polythiazole
Adding 1.2g of crystalline flake graphite and 5g of phosphoric acid into a three-neck flask, placing the three-neck flask into an ice-water bath, slowly adding 20mL of concentrated sulfuric acid, magnetically stirring for 10min, slowly adding 1.8g of potassium permanganate, and reacting for 2 h. And heating to 50 ℃, continuing to react for 1h, cooling to room temperature, adding 100mL of ice water into the reaction solution, stirring, dropwise adding 1mL of hydrogen peroxide (with the mass concentration of 30%), performing suction filtration, washing and vacuum drying to obtain the graphene oxide.
And adding 0.3g of graphene oxide into a 30mL pressure reaction kettle, then adding concentrated ammonia water, reacting for 6 hours at 95 ℃, cooling, performing suction filtration, washing with distilled water, and performing vacuum drying to obtain the amino modified graphene oxide. Adding 0.3g of amino modified graphene oxide, 2mL of isopropanol, 15mL of distilled water, 40mL of 2mol/mL hydrochloric acid solution and 0.5g of thiazole into a three-neck flask, placing the three-neck flask into an ice-water bath, slowly adding 10g of ammonium persulfate aqueous solution with the mass concentration of 10%, and stirring for reacting for 6 hours. And (4) carrying out suction filtration, washing and vacuum drying to obtain the graphene oxide grafted polythiazole.
4) Preparation of nitrogen and sulfur co-doped graphene-based composite porous aerogel material
And (3) dispersing 0.03g of polyacrylonitrile porous nanofiber and 0.02 g of graphene oxide grafted benzothiazole in 200mL of deionized water, performing ultrasonic dispersion for 30min, adding 0.1g of ZIF-8 into the dispersion liquid after the ultrasonic treatment is finished, and performing continuous ultrasonic dispersion and stirring to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 dispersion liquid. Pouring the polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 dispersion liquid into a mold, freezing in liquid nitrogen at-196 ℃ for 20min, and drying in a freeze dryer for 24h after the freezing is finished to obtain the polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 aerogel. Placing polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 aerogel in a tubular furnace, heating from 25 ℃ to 290 ℃ under the protection of nitrogen, preserving heat for 2 hours, then heating from 290 ℃ to 960 ℃, and preserving heat for 11 hours to finally obtain the carbon fiber/nitrogen and sulfur co-doped graphene/porous carbon composite porous aerogel, namely the nitrogen and sulfur co-doped graphene-based composite porous aerogel material.
The nitrogen and 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 482m2(iv) g. The specific capacitance of the electrode material is 333F/g under the condition that the current density is 1A/g.
Comparative example 1
Different from the embodiment 1, in the step 1), the addition amount of tetraethyl orthosilicate is 0, and finally the carbon fiber/nitrogen and sulfur co-doped graphene composite porous aerogel is obtained. The porosity of the aerogel electrode material is 90.1%, and the specific surface area is 408m2(ii) in terms of/g. The specific capacitance of the electrode material is 280F/g under the condition that the current density is 1A/g.
Comparative example 2
The method is different from the embodiment 1 in that in the step 4), the graphene oxide grafted polythiazole is replaced by graphene oxide, and finally the carbon fiber/graphene oxide/ZIF-8 composite porous aerogel is obtained. The aerogel electrode material has the porosity of 95.1 percent and the specific surface area of511m2(ii) in terms of/g. The specific capacitance of the electrode material is 271F/g under the condition that the current density is 1A/g.
Comparative example 3
The difference from the embodiment 1 is that in the step 4), the "polyacrylonitrile porous nanofiber" is replaced by the commercially purchased "polyacrylonitrile powder", and finally the carbon/nitrogen and sulfur co-doped graphene oxide/ZIF-8 composite porous aerogel is obtained. The aerogel electrode material has the porosity of 88.1 percent and the specific surface area of 310m2(iv) g. The specific capacitance of the electrode material is 261F/g under the condition that the current density is 1A/g.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (8)
1. The preparation method of the nitrogen and 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, then adding polyvinylpyrrolidone, stirring for reaction, standing, centrifuging, drying, heating the product from 25 ℃ to 300-350 ℃ at the speed of 5-10 ℃/min under the protection of nitrogen, keeping the temperature for 3-5 h, and naturally cooling to obtain a ZIF-8 metal organic frame;
preparing graphene oxide grafted polythiazole;
dispersing the polyacrylonitrile porous nanofiber and the graphene oxide grafted benzothiazole in deionized water, then adding a ZIF-8 metal organic frame, and continuously performing ultrasonic dispersion and stirring to obtain a polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 dispersion liquid;
pouring the polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 dispersion liquid into a mold, and sequentially carrying out liquid nitrogen freezing treatment and freeze drying to obtain polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 aerogel;
the method comprises the steps of heating polyacrylonitrile porous nanofiber/graphene oxide grafted thiazole/ZIF-8 aerogel from 25 ℃ to 250-300 ℃ under the protection of nitrogen, preserving heat for 2-3 hours, heating from 250-300 ℃ to 900-1000 ℃, and preserving heat for 10-15 hours to obtain carbon fiber/nitrogen and sulfur co-doped graphene/porous carbon composite porous aerogel, namely the nitrogen and sulfur co-doped graphene-based composite porous aerogel material.
2. The preparation method of the nitrogen and sulfur co-doped graphene-based composite porous aerogel of claim 1, wherein the preparation method of the polyacrylonitrile porous nanofiber comprises the following steps:
dissolving polyacrylonitrile in dimethyl sulfoxide, and adding tetraethyl orthosilicate and glacial acetic acid to obtain a precursor solution;
freezing the precursor solution at-40 to-10 ℃ for 100 to 200min, removing the solvent, and freeze-drying to obtain 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.
3. The preparation method of the nitrogen and sulfur co-doped graphene-based composite porous aerogel according to claim 2, wherein in the precursor solution, the mass concentration of polyacrylonitrile is 4-8%, and the mass concentration of tetraethyl orthosilicate is 0.4-1%.
4. The preparation method of the nitrogen and sulfur co-doped graphene-based composite porous aerogel according to claim 1, wherein the mass ratio of the zinc nitrate to the 2-methylimidazole is (2-4): (5-15).
5. The preparation method of the nitrogen and sulfur co-doped graphene-based composite porous aerogel of claim 1, wherein 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 ℃, continuing to react for 1 hour, cooling to room temperature, adding ice water, stirring, dropwise adding hydrogen peroxide, performing suction filtration, washing and vacuum drying to obtain graphene oxide;
dispersing the graphene oxide in strong ammonia water, carrying out hydrothermal reaction at 95 ℃, carrying out suction filtration, washing with distilled water, and vacuum drying to obtain amino modified graphene oxide;
and (3) 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 an ice water bath, and reacting for 6 hours to obtain the graphene oxide grafted benzothiazole.
6. The preparation method of the nitrogen and 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).
7. The preparation method of the nitrogen and sulfur co-doped graphene-based composite porous aerogel of claim 1, wherein the mass ratio of the polyacrylonitrile porous nanofiber, the graphene oxide grafted benzothiazole and the ZIF-8 metal organic framework is (2-3): (1-2): (4-6).
8. A composite porous aerogel material obtained by the preparation method of any one of claims 1 to 7.
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