CN111777791A - Preparation method and application of graphene/polyacrylonitrile nanofiber composite aerogel - Google Patents
Preparation method and application of graphene/polyacrylonitrile nanofiber composite aerogel Download PDFInfo
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Abstract
The invention discloses a preparation method of graphene/polyacrylonitrile nanofiber composite aerogel, belonging to the field of graphene aerogel, and specifically comprising the following steps: preparing a graphene oxide solution with a certain concentration, and modifying the graphene oxide solution to introduce a nitrile group; then mixing the nitrile group modified graphene oxide solution and the polyacrylonitrile nanofiber dispersion liquid, and performing ultrasonic dispersion; carrying out freeze drying, pre-oxidation and hydrothermal reduction on the nitrile group modified graphene oxide/polyacrylonitrile nanofiber mixed solution to obtain graphene/polyacrylonitrile nanofiber composite hydrogel; and (3) carrying out freeze drying on the graphene/polyacrylonitrile nanofiber composite hydrogel to prepare the graphene/polyacrylonitrile nanofiber composite aerogel. The preparation process is nontoxic and environment-friendly, and the obtained aerogel has the advantages of large specific surface area, good rebound resilience, stable structure and the like, and can be used for preparing electrode materials of super capacitors or batteries.
Description
Technical Field
The invention belongs to the technical field of graphene aerogel, and particularly relates to a preparation method and application of graphene/polyacrylonitrile nanofiber composite aerogel.
Background
The aerogel has the advantages of high porosity, large specific surface area, good conductivity and the like, is widely used for adsorbing materials, hydrogen storage materials, heat insulation materials and the like, particularly has potential application value in the field of electrode materials because the pore size distribution can be effectively regulated and controlled by a physical or chemical method.
Graphene is a carbon atom through sp2The two-dimensional material which is formed by the hybrid tracks and has a single-layer sheet structure in a hexagonal honeycomb lattice shape has a perfect two-dimensional crystal structure. The graphene has excellent physical and chemical properties such as good conductivity, strong charge transmission capability, large specific surface area, high specific strength and stable performance, and is widely applied to the fields of energy storage, catalysis, communication, functional composite materials and the like. Particularly as an electrode materialHigh specific energy and prolonged service life. In practical application, graphene is easy to agglomerate, so that the specific surface area of the graphene is difficult to reach an ideal level, and the specific capacitance is low. Therefore, the graphene aerogel with a three-dimensional structure can be prepared, so that agglomeration is reduced, and the specific surface area and specific capacity are improved.
The nano-fiber is a good choice for preparing electrode materials due to the high specific surface area. The electrostatic spinning method is the simplest method for preparing the nanofiber, so that the polyacrylonitrile nanofiber can be prepared by the electrostatic spinning method and compounded with the graphene oxide to be used for an electrode material, so that the specific surface area of the polyacrylonitrile nanofiber is further increased, and the specific capacitance of the electrode material is improved. The polyacrylonitrile nano-fiber exists in a composite aerogel system in a continuous long fiber form, can play a certain reinforcing role on the aerogel, and is beneficial to prolonging the service life of the electrode material.
Disclosure of Invention
The invention aims to provide a preparation method and application of graphene/polyacrylonitrile nanofiber composite aerogel. According to the invention, firstly, the oxidized graphene is subjected to nitrile modification, and then the oxidized graphene and polyacrylonitrile nanofiber are compounded to prepare the graphene/polyacrylonitrile nanofiber composite aerogel through the processes of freeze drying, pre-oxidation, hydrothermal reduction, freeze drying and the like. The invention can improve the specific surface area of the graphene/polyacrylonitrile nanofiber composite aerogel and reduce the occurrence of graphene agglomeration; and meanwhile, more active sites are provided, so that more ions can be adsorbed, and the specific capacitance is improved. In addition, in the pre-oxidation process, the nitrile modified graphene oxide and polyacrylonitrile are subjected to cyclization reaction. On one hand, a conjugated structure formed by cyclization reaction is beneficial to ion transmission, so that the conductivity can be improved; on the other hand, the annular structure is stable, the volume change in the charge-discharge process can be reduced, and the service life can be prolonged. Therefore, the preparation of the graphene/polyacrylonitrile nanofiber composite aerogel can effectively improve the comprehensive performance of the electrode material of the supercapacitor or the battery.
The preparation process of the graphene/polyacrylonitrile nanofiber composite aerogel provided by the invention comprises the following steps: preparing a graphene oxide solution with a certain concentration, and performing nitrile modification on the graphene oxide solution; then preparing polyacrylonitrile nano-fiber by an electrostatic spinning method, and collecting the polyacrylonitrile nano-fiber in absolute ethyl alcohol to obtain polyacrylonitrile nano-fiber dispersion liquid; and mixing the modified graphene oxide solution with the polyacrylonitrile nanofiber dispersion solution, performing ultrasonic dispersion, and performing freeze drying, pre-oxidation, hydrothermal reduction and freeze drying to prepare the graphene/polyacrylonitrile nanofiber composite aerogel.
The specific preparation steps of the graphene/polyacrylonitrile nanofiber composite aerogel provided by the invention are as follows:
(1) dispersing graphene oxide in a solvent, and performing ultrasonic dispersion to obtain a stable Graphene Oxide (GO) solution;
(2) carrying out nitrile modification on the graphene oxide solution to obtain a modified graphene oxide (m-GO) solution;
(3) dissolving Polyacrylonitrile (PAN), heating and stirring to obtain a uniform light yellow viscous solution, preparing nanofiber from the polyacrylonitrile solution through electrostatic spinning, and collecting the nanofiber in absolute ethyl alcohol to obtain polyacrylonitrile nanofiber dispersion liquid;
(4) mixing the modified graphene oxide with a polyacrylonitrile nanofiber dispersion solution, and performing ultrasonic dispersion to obtain a modified graphene oxide/polyacrylonitrile (m-GO/PAN) nanofiber mixed solution;
(5) preparing a graphene oxide/polyacrylonitrile (GO/PAN) nanofiber composite material by carrying out freeze drying and pre-oxidation on the obtained m-GO/PAN nanofiber mixed solution;
(6) preparing graphene/polyacrylonitrile (G/PAN) nanofiber composite hydrogel from the obtained GO-PAN nanofiber composite material through hydrothermal reduction;
(7) and freeze-drying the obtained G/PAN nanofiber composite hydrogel to obtain the G/PAN nanofiber composite aerogel.
Further, in the step (1) of the invention, the solvent of the graphene oxide solution is water or organic solvents such as N' N-dimethylformamide and dimethyl sulfoxide, the concentration of the graphene oxide solution is 2-4 mg/mL, and the ultrasonic dispersion time is 2-3 h.
Further, in the step (2) of the present invention, the cyanation modification is a reaction between a substance containing both hydroxyl and nitrile groups or both carboxyl and nitrile groups and graphene oxide, and the molecular formula is:
Wherein R is1Is straight-chain, branched or cyclic C1-C21Alkyl, aryl, alkenyl, alkynyl, etc.; r2Is straight-chain, branched or cyclic C1-C21Alkylene, alkenyl, etc.
Respectively is that
For example, the nitrile modification process is as follows:
further, the solvent of the polyacrylonitrile spinning solution in the step (3) is N' N-dimethylformamide, dimethyl sulfoxide and the like, and the concentration of the polyacrylonitrile spinning solution is 0.08-0.12 g/mL; the heating temperature is 50-70 ℃.
Further, in the electrostatic spinning process described in the step (3), the spinning conditions are as follows: the spinning speed is 0.25-0.4 mm/min, and the receiving distance is 15-20 cm. The concentration of the polyacrylonitrile nano-fiber dispersion liquid is 0.1-0.25 mg/mL.
Further, the mass ratio of the m-GO in the step (4) to the PAN nano-fiber in the step (3) is 20: 1-5, and the ultrasonic dispersion time is 2-3 h.
Further, in the step (5), the freeze drying temperature is-70 to-50 ℃, and the time is 24 to 36 hours; the pre-oxidation temperature is 200-280 ℃, and the time is 2-4 h.
Respectively is that
For example, the pre-oxidation process is as follows:
further, the hydrothermal reduction temperature in the step (6) of the invention is 150-200 ℃, preferably 180 ℃; the hydrothermal reduction time is 12-24 h.
Further, the freeze-drying temperature in the step (7) of the invention is-80 to-50 ℃, preferably-70 ℃; the freeze drying time is 36-48 h.
Compared with the prior art, the invention has the advantages that:
(1) the preparation process is nontoxic, and the preparation method is a green and environment-friendly preparation method of the graphene-based aerogel.
(2) The polyacrylonitrile is low in price, the diameter of the nanofiber prepared by electrostatic spinning is controllable, and the specific surface area of the aerogel can be increased.
(3) The nitrile group modified graphene oxide and polyacrylonitrile nano-fibers form a ring-shaped stable structure in the pre-oxidation process, so that the conductivity of the graphene can be improved, and the service life of the graphene aerogel can be prolonged.
(4) The graphene/polyacrylonitrile nanofiber composite aerogel prepared by the method can be used as an electrode material of a super capacitor or a battery.
Detailed Description
The invention is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. In addition, after reading the teaching of the present invention, those skilled in the art can make various changes or modifications to the invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1
The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel of the embodiment is as follows:
(1) preparing a graphene oxide aqueous solution with the concentration of 2mg/mL, and carrying out ultrasonic treatment for 2h to uniformly disperse the graphene oxide aqueous solution;
(2) selecting 3-hydroxy-butyronitrile to carry out nitrile modification on graphene oxide, wherein the reaction temperature is 70 ℃, and reacting for 12 hours;
(3) adding 0.8g of polyacrylonitrile powder into 10mL of N' N-dimethylformamide solution, heating and stirring to obtain uniform and viscous polyacrylonitrile solution; performing electrostatic spinning on polyacrylonitrile solution, wherein the spinning speed is 0.3mm/min, the receiving distance is 15cm, and collecting the polyacrylonitrile solution in absolute ethyl alcohol to obtain polyacrylonitrile nano-fiber dispersion liquid with the concentration of 0.1 mg/mL;
(4) mixing the modified graphene oxide aqueous solution with a polyacrylonitrile nanofiber dispersion solution, wherein the mass ratio of the modified graphene oxide to the PAN nanofiber is 20:3, and uniformly dispersing by ultrasonic for 2 hours;
(5) freeze-drying the modified mixed solution of the graphene oxide aqueous solution and the polyacrylonitrile nano-fiber at-50 ℃ for 36h, and then pre-oxidizing at 260 ℃ for 2h to obtain a graphene oxide/polyacrylonitrile nano-fiber composite material;
(6) placing the graphene oxide/polyacrylonitrile nanofiber composite material in a hydrothermal kettle, and carrying out hydrothermal reduction for 12 hours at 180 ℃ to obtain graphene/polyacrylonitrile nanofiber composite hydrogel;
(7) and (3) freeze-drying the graphene/polyacrylonitrile nanofiber composite hydrogel for 36 hours at the temperature of-70 ℃ in a freeze dryer to obtain the graphene/polyacrylonitrile nanofiber composite aerogel.
The specific capacitance of the graphene/polyacrylonitrile nanofiber composite aerogel can reach 280F/g.
Comparative example 1
The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel comprises the following steps:
(1) preparing a graphene oxide aqueous solution with the concentration of 2mg/mL, and carrying out ultrasonic treatment for 2h to uniformly disperse the graphene oxide aqueous solution;
(2) adding 0.8g of polyacrylonitrile powder into 10mL of N' N-dimethylformamide solution, heating and stirring to obtain uniform and viscous polyacrylonitrile solution; performing electrostatic spinning on polyacrylonitrile solution, wherein the spinning speed is 0.3mm/min, the receiving distance is 15cm, and collecting the polyacrylonitrile solution in absolute ethyl alcohol to obtain polyacrylonitrile nano-fiber dispersion liquid with the concentration of 0.1 mg/mL;
(3) mixing the graphene oxide aqueous solution with the polyacrylonitrile nanofiber dispersion liquid, wherein the mass ratio of the graphene oxide to the PAN nanofiber is 20:3, and uniformly dispersing by ultrasonic for 2 hours;
(4) freeze-drying the mixed solution of the graphene oxide aqueous solution and the polyacrylonitrile nano-fiber at-50 ℃ for 36h, and then pre-oxidizing at 260 ℃ for 2h to obtain a graphene oxide/polyacrylonitrile nano-fiber composite material;
(5) placing the graphene oxide/polyacrylonitrile nanofiber composite material in a hydrothermal kettle, and carrying out hydrothermal reduction for 12 hours at 180 ℃ to obtain graphene/polyacrylonitrile nanofiber composite hydrogel;
(6) and (3) freeze-drying the graphene/polyacrylonitrile nanofiber composite hydrogel for 36 hours at the temperature of-70 ℃ in a freeze dryer to obtain the graphene/polyacrylonitrile nanofiber composite aerogel.
The specific capacitance of the graphene/polyacrylonitrile nanofiber composite aerogel is 240F/g.
Example 2
The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel comprises the following steps:
(1) preparing a graphene oxide aqueous solution with the concentration of 3mg/mL, and carrying out ultrasonic treatment for 2h to uniformly disperse the graphene oxide aqueous solution;
(2) selecting 3-hydroxy-butyronitrile to carry out nitrile modification on graphene oxide, wherein the reaction temperature is 80 ℃, and reacting for 6 hours;
(3) adding 1g of polyacrylonitrile powder into 10mL of N' N-dimethylformamide solution, heating and stirring to obtain uniform and viscous polyacrylonitrile solution; performing electrostatic spinning on polyacrylonitrile solution, wherein the spinning speed is 0.35mm/min, the receiving distance is 15cm, and collecting the polyacrylonitrile solution in absolute ethyl alcohol to obtain polyacrylonitrile nano-fiber dispersion liquid with the concentration of 0.2 mg/mL;
(4) mixing the modified graphene oxide aqueous solution with a polyacrylonitrile nanofiber dispersion solution, wherein the mass ratio of the modified graphene oxide to the PAN nanofiber is 20:2, and uniformly dispersing by ultrasonic for 2 hours;
(5) freeze-drying the modified mixed solution of the graphene oxide aqueous solution and the polyacrylonitrile nano-fiber at-60 ℃ for 32h, and then pre-oxidizing at 280 ℃ for 2h to obtain a graphene oxide/polyacrylonitrile nano-fiber composite material;
(6) placing the graphene oxide/polyacrylonitrile nanofiber composite material in a hydrothermal kettle, and carrying out hydrothermal reduction for 16h at 180 ℃ to obtain graphene/polyacrylonitrile nanofiber composite hydrogel;
(7) and (3) freeze-drying the graphene/polyacrylonitrile nanofiber composite hydrogel for 40h at-70 ℃ in a freeze dryer to obtain the graphene/polyacrylonitrile nanofiber composite aerogel.
The specific capacitance of the graphene/polyacrylonitrile nanofiber composite aerogel can reach 260F/g.
Comparative example 2
The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel comprises the following steps:
(1) preparing a graphene oxide aqueous solution with the concentration of 3mg/mL, and carrying out ultrasonic treatment for 2h to uniformly disperse the graphene oxide aqueous solution;
(2) adding 1g of polyacrylonitrile powder into 10mL of N' N-dimethylformamide solution, heating and stirring to obtain uniform and viscous polyacrylonitrile solution; performing electrostatic spinning on polyacrylonitrile solution, wherein the spinning speed is 0.35mm/min, the receiving distance is 15cm, and collecting the polyacrylonitrile solution in absolute ethyl alcohol to obtain polyacrylonitrile nano-fiber dispersion liquid with the concentration of 0.2 mg/mL;
(3) mixing the graphene oxide aqueous solution with the polyacrylonitrile nanofiber dispersion liquid, wherein the mass ratio of the graphene oxide to the PAN nanofiber is 20:2, and uniformly dispersing by ultrasonic for 2 hours;
(4) freeze-drying the mixed solution of the graphene oxide aqueous solution and the polyacrylonitrile nano-fiber at-60 ℃ for 32h, and then pre-oxidizing at 280 ℃ for 2h to obtain a graphene oxide/polyacrylonitrile nano-fiber composite material;
(5) placing the graphene oxide/polyacrylonitrile nanofiber composite material in a hydrothermal kettle, and carrying out hydrothermal reduction for 16h at 180 ℃ to obtain graphene/polyacrylonitrile nanofiber composite hydrogel;
(6) and (3) freeze-drying the graphene/polyacrylonitrile nanofiber composite hydrogel for 40h at-70 ℃ in a freeze dryer to obtain the graphene/polyacrylonitrile nanofiber composite aerogel.
The specific capacitance of the graphene/polyacrylonitrile nanofiber composite aerogel is 220F/g.
Example 3
The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel of the embodiment is as follows:
(1) preparing a graphene oxide aqueous solution with the concentration of 4mg/mL, and carrying out ultrasonic treatment for 3h to uniformly disperse the graphene oxide aqueous solution;
(2) selecting 2-hydroxy-3-methyl-3-butenenitrile to perform nitrile modification on graphene oxide, wherein the reaction temperature is 65 ℃, and reacting for 16 hours;
(3) adding 1.2g of polyacrylonitrile powder into 10mL of N' N-dimethylformamide solution, heating and stirring to obtain uniform and viscous polyacrylonitrile solution; performing electrostatic spinning on polyacrylonitrile solution, wherein the spinning speed is 0.4mm/min, the receiving distance is 20cm, and collecting the polyacrylonitrile solution in absolute ethyl alcohol to obtain polyacrylonitrile nano-fiber dispersion liquid with the concentration of 0.25 mg/mL;
(4) mixing the modified graphene oxide aqueous solution with a polyacrylonitrile nanofiber dispersion solution, wherein the mass ratio of the modified graphene oxide to the PAN nanofiber is 20:5, and uniformly dispersing by ultrasonic for 3 hours;
(5) freeze-drying the modified mixed solution of the graphene oxide aqueous solution and the polyacrylonitrile nano-fiber at-70 ℃ for 28h, and then pre-oxidizing at 240 ℃ for 3h to obtain a graphene oxide/polyacrylonitrile nano-fiber composite material;
(6) placing the graphene oxide/polyacrylonitrile nanofiber composite material in a hydrothermal kettle, and carrying out hydrothermal reduction for 24 hours at 180 ℃ to obtain graphene/polyacrylonitrile nanofiber composite hydrogel;
(7) and (3) freeze-drying the graphene/polyacrylonitrile nanofiber composite hydrogel for 48 hours at the temperature of-70 ℃ in a freeze dryer to obtain the graphene/polyacrylonitrile nanofiber composite aerogel.
The specific capacitance of the graphene/polyacrylonitrile nanofiber composite aerogel can reach 250F/g.
Comparative example 3
The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel comprises the following steps:
(1) preparing a graphene oxide aqueous solution with the concentration of 4mg/mL, and carrying out ultrasonic treatment for 3h to uniformly disperse the graphene oxide aqueous solution;
(2) adding 1.2g of polyacrylonitrile powder into 10mL of N' N-dimethylformamide solution, heating and stirring to obtain uniform and viscous polyacrylonitrile solution; performing electrostatic spinning on polyacrylonitrile solution, wherein the spinning speed is 0.4mm/min, the receiving distance is 20cm, and collecting the polyacrylonitrile solution in absolute ethyl alcohol to obtain polyacrylonitrile nano-fiber dispersion liquid with the concentration of 0.25 mg/mL;
(3) mixing the graphene oxide aqueous solution with the polyacrylonitrile nanofiber dispersion liquid, wherein the mass ratio of the graphene oxide to the PAN nanofiber is 20:5, and uniformly dispersing by ultrasonic treatment for 3 hours;
(4) freeze-drying the mixed solution of the graphene oxide aqueous solution and the polyacrylonitrile nano-fiber at-70 ℃ for 28h, and then pre-oxidizing at 240 ℃ for 3h to obtain a graphene oxide/polyacrylonitrile nano-fiber composite material;
(5) placing the graphene oxide/polyacrylonitrile nanofiber composite material in a hydrothermal kettle, and carrying out hydrothermal reduction for 24 hours at 180 ℃ to obtain graphene/polyacrylonitrile nanofiber composite hydrogel;
(6) and (3) freeze-drying the graphene/polyacrylonitrile nanofiber composite hydrogel for 48 hours at the temperature of-70 ℃ in a freeze dryer to obtain the graphene/polyacrylonitrile nanofiber composite aerogel.
The specific capacitance of the graphene/polyacrylonitrile nanofiber composite aerogel is 220F/g.
Example 4
The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel of the embodiment is as follows:
(1) dissolving graphene oxide in N' N-dimethylformamide, preparing a graphene oxide solution with the concentration of 4mg/mL, performing ultrasonic treatment for 3 hours, and uniformly dispersing;
(2) selecting 2-hydroxy-3-methyl-3-butenenitrile to perform nitrile modification on graphene oxide, wherein the reaction temperature is 60 ℃, and reacting for 24 hours;
(3) adding 1.1g of polyacrylonitrile powder into 10mL of N' N-dimethylformamide solution, heating and stirring to obtain uniform and viscous polyacrylonitrile solution; performing electrostatic spinning on polyacrylonitrile solution, wherein the spinning speed is 0.4mm/min, the receiving distance is 20cm, and collecting the polyacrylonitrile solution in absolute ethyl alcohol to obtain polyacrylonitrile nano-fiber dispersion liquid with the concentration of 0.2 mg/mL;
(4) mixing the modified graphene oxide aqueous solution with a polyacrylonitrile nanofiber dispersion solution, wherein the mass ratio of the modified graphene oxide to the PAN nanofiber is 20:4, and uniformly dispersing by ultrasonic for 3 hours;
(5) freeze-drying the modified mixed solution of the graphene oxide aqueous solution and the polyacrylonitrile nano-fiber at-70 ℃ for 36h, and then pre-oxidizing at 220 ℃ for 3h to obtain a graphene oxide/polyacrylonitrile nano-fiber composite material;
(6) placing the graphene oxide/polyacrylonitrile nanofiber composite material in a hydrothermal kettle, and carrying out hydrothermal reduction for 24 hours at 180 ℃ to obtain graphene/polyacrylonitrile nanofiber composite hydrogel;
(7) and (3) freeze-drying the graphene/polyacrylonitrile nanofiber composite hydrogel for 48 hours at the temperature of-70 ℃ in a freeze dryer to obtain the graphene/polyacrylonitrile nanofiber composite aerogel.
The specific capacitance of the graphene/polyacrylonitrile nanofiber composite aerogel can reach 270F/g.
Comparative example 4
The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel comprises the following steps:
(1) dissolving graphene oxide in N' N-dimethylformamide, preparing a graphene oxide solution with the concentration of 4mg/mL, performing ultrasonic treatment for 3 hours, and uniformly dispersing;
(2) adding 1.1g of polyacrylonitrile powder into 10mL of N' N-dimethylformamide solution, heating and stirring to obtain uniform and viscous polyacrylonitrile solution; performing electrostatic spinning on polyacrylonitrile solution, wherein the spinning speed is 0.4mm/min, the receiving distance is 20cm, and collecting the polyacrylonitrile solution in absolute ethyl alcohol to obtain polyacrylonitrile nano-fiber dispersion liquid with the concentration of 0.2 mg/mL;
(3) mixing the graphene oxide aqueous solution with the polyacrylonitrile nanofiber dispersion liquid, wherein the mass ratio of the modified graphene oxide to the PAN nanofiber is 20:4, and uniformly dispersing by ultrasonic for 3 hours;
(4) freeze-drying the mixed solution of the graphene oxide aqueous solution and the polyacrylonitrile nano-fiber at-70 ℃ for 36h, and then pre-oxidizing at 220 ℃ for 3h to obtain a graphene oxide/polyacrylonitrile nano-fiber composite material;
(5) placing the graphene oxide/polyacrylonitrile nanofiber composite material in a hydrothermal kettle, and carrying out hydrothermal reduction for 24 hours at 180 ℃ to obtain graphene/polyacrylonitrile nanofiber composite hydrogel;
(6) and (3) freeze-drying the graphene/polyacrylonitrile nanofiber composite hydrogel for 48 hours at the temperature of-70 ℃ in a freeze dryer to obtain the graphene/polyacrylonitrile nanofiber composite aerogel.
The specific capacitance of the graphene/polyacrylonitrile nanofiber composite aerogel is 235F/g.
Example 5
The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel of the embodiment is as follows:
(1) dissolving graphene oxide in N' N-dimethylformamide, preparing a graphene oxide solution with the concentration of 2mg/mL, and performing ultrasonic treatment for 2 hours to uniformly disperse the graphene oxide solution;
(2) selecting 2-hydroxy-3-methyl-3-butenenitrile to perform nitrile modification on graphene oxide, wherein the reaction temperature is 75 ℃, and reacting for 8 hours;
(3) adding 0.9g of polyacrylonitrile powder into 10mL of N' N-dimethylformamide solution, heating and stirring to obtain uniform and viscous polyacrylonitrile solution; performing electrostatic spinning on polyacrylonitrile solution, wherein the spinning speed is 0.25mm/min, the receiving distance is 15cm, and collecting the polyacrylonitrile solution in absolute ethyl alcohol to obtain polyacrylonitrile nano-fiber dispersion liquid with the concentration of 0.15 mg/mL;
(4) mixing the modified graphene oxide aqueous solution with a polyacrylonitrile nanofiber dispersion solution, wherein the mass ratio of the modified graphene oxide to the PAN nanofiber is 20:1, and uniformly dispersing by ultrasonic for 2 hours;
(5) freeze-drying the modified mixed solution of the graphene oxide aqueous solution and the polyacrylonitrile nano-fiber at-70 ℃ for 24h, and then pre-oxidizing at 200 ℃ for 4h to obtain a graphene oxide/polyacrylonitrile nano-fiber composite material;
(6) placing the graphene oxide/polyacrylonitrile nanofiber composite material in a hydrothermal kettle, and carrying out hydrothermal reduction for 20 hours at 180 ℃ to obtain graphene/polyacrylonitrile nanofiber composite hydrogel;
(7) and (3) freeze-drying the graphene/polyacrylonitrile nanofiber composite hydrogel for 44 hours at the temperature of minus 70 ℃ in a freeze dryer to obtain the graphene/polyacrylonitrile nanofiber composite aerogel.
The specific capacitance of the graphene/polyacrylonitrile nanofiber composite aerogel can reach 250F/g.
Comparative example 5
The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel comprises the following steps:
(1) dissolving graphene oxide in N' N-dimethylformamide, preparing a graphene oxide solution with the concentration of 2mg/mL, and performing ultrasonic treatment for 2 hours to uniformly disperse the graphene oxide solution;
(2) adding 0.9g of polyacrylonitrile powder into 10mL of N' N-dimethylformamide solution, heating and stirring to obtain uniform and viscous polyacrylonitrile solution; performing electrostatic spinning on polyacrylonitrile solution, wherein the spinning speed is 0.25mm/min, the receiving distance is 15cm, and collecting the polyacrylonitrile solution in absolute ethyl alcohol to obtain polyacrylonitrile nano-fiber dispersion liquid with the concentration of 0.15 mg/mL;
(3) mixing the graphene oxide aqueous solution with the polyacrylonitrile nanofiber dispersion liquid, wherein the mass ratio of the graphene oxide to the PAN nanofiber is 20:1, and uniformly dispersing by ultrasonic for 2 hours;
(4) freeze-drying the mixed solution of the graphene oxide aqueous solution and the polyacrylonitrile nano-fiber at-70 ℃ for 24h, and then pre-oxidizing at 200 ℃ for 4h to obtain a graphene oxide/polyacrylonitrile nano-fiber composite material;
(5) placing the graphene oxide/polyacrylonitrile nanofiber composite material in a hydrothermal kettle, and carrying out hydrothermal reduction for 20 hours at 180 ℃ to obtain graphene/polyacrylonitrile nanofiber composite hydrogel;
(6) and (3) freeze-drying the graphene/polyacrylonitrile nanofiber composite hydrogel for 44 hours at the temperature of minus 70 ℃ in a freeze dryer to obtain the graphene/polyacrylonitrile nanofiber composite aerogel.
The specific capacitance of the graphene/polyacrylonitrile nanofiber composite aerogel is 210F/g.
Claims (10)
1. A preparation method of graphene/polyacrylonitrile nanofiber composite aerogel is characterized by comprising the following steps:
(1) dispersing graphene oxide in a solvent, and performing ultrasonic dispersion to obtain a stable Graphene Oxide (GO) solution;
(2) carrying out nitrile modification on the graphene oxide solution to obtain a modified graphene oxide (m-GO) solution;
(3) heating and dissolving Polyacrylonitrile (PAN), preparing PAN nano-fiber by adopting an electrostatic spinning method, and dispersing the PAN nano-fiber in absolute ethyl alcohol to obtain polyacrylonitrile nano-fiber dispersion liquid;
(4) mixing the m-GO solution obtained in the step (2) with the PAN nanofiber dispersion liquid obtained in the step (3), and performing ultrasonic dispersion to obtain a modified graphene oxide/polyacrylonitrile (m-GO/PAN) nanofiber mixed solution;
(5) preparing a graphene oxide/polyacrylonitrile (GO/PAN) nanofiber composite material by freezing, drying and pre-oxidizing the m-GO/PAN mixed solution obtained in the step (4);
(6) carrying out hydrothermal reduction on the GO/PAN composite material obtained in the step (5) to prepare graphene/polyacrylonitrile (G/PAN) nanofiber composite hydrogel;
(7) and (4) freeze-drying the G/PAN nanofiber composite hydrogel obtained in the step (6) to obtain the G/PAN nanofiber composite aerogel.
2. The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel according to claim 1, which is characterized in that: the solvent in the step (1) is water or an organic solvent, the concentration of the graphene oxide solution is 2-4 mg/mL, and the ultrasonic dispersion time is 2-3 h.
3. The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel according to claim 1, which is characterized in that: the nitrile modification in the step (2) is to select a substance containing both hydroxyl and nitrile groups or both carboxyl and nitrile groups to react with graphene oxide, and the molecular formula of the substance is as follows:
4. the preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel according to claim 1, which is characterized in that: the solvent of the polyacrylonitrile spinning solution in the step (3) is N' N-dimethylformamide and dimethyl sulfoxide, and the concentration of the polyacrylonitrile spinning solution is 0.08-0.12 g/mL; the heating temperature is 50-70 ℃; the concentration of the polyacrylonitrile nano-fiber dispersion liquid is 0.1-0.25 mg/mL.
5. The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel according to claim 1, which is characterized in that: the mass ratio of m-GO in the step (4) to PAN nano-fiber in the step (3) is 20 (1-5), and the ultrasonic dispersion time is 2-3 h.
6. The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel according to claim 1, which is characterized in that: the freeze drying temperature in the step (5) is-70 to-50 ℃, and the time is 24 to 36 hours; the pre-oxidation temperature is 200-280 ℃, and the time is 2-4 h.
7. The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel according to claim 1, which is characterized in that: the hydrothermal reduction temperature in the step (6) is 150-200 ℃, and the time is 12-24 hours.
8. The preparation method of the graphene/polyacrylonitrile nanofiber composite aerogel according to claim 1, which is characterized in that: the freeze drying temperature in the step (7) is-80 to-50 ℃, and the time is 36 to 48 hours.
9. Graphene/polyacrylonitrile nanofiber composite aerogel prepared by the method of any one of claims 1 to 8.
10. Use of the graphene/polyacrylonitrile nanofiber composite aerogel according to claim 9 as an electrode material of a supercapacitor or battery.
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