CN108570229B - Graphene nanoribbon-polyaniline nanoribbon composite material and preparation method thereof - Google Patents
Graphene nanoribbon-polyaniline nanoribbon composite material and preparation method thereof Download PDFInfo
- Publication number
- CN108570229B CN108570229B CN201810435311.9A CN201810435311A CN108570229B CN 108570229 B CN108570229 B CN 108570229B CN 201810435311 A CN201810435311 A CN 201810435311A CN 108570229 B CN108570229 B CN 108570229B
- Authority
- CN
- China
- Prior art keywords
- nanoribbon
- polyaniline
- graphene
- composite material
- graphene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a graphene nanoribbon-polyaniline nanoribbon composite material and a preparation method thereof, which comprises the steps of dispersing graphene nanoribbons in water, adding a surfactant, carrying out hydrothermal reaction to obtain graphene oxide nanoribbon hydrogel, soaking the graphene oxide nanoribbon hydrogel in a solution in which aniline is dissolved for a period of time, polymerizing aniline at a low temperature, and reducing by a reducing agent to obtain the graphene nanoribbon-polyaniline nanoribbon composite material, wherein the product is composite aerogel with a network interpenetrating structure formed by the graphene nanoribbons and the polyaniline nanoribbons, the specific capacitance of the graphene nanoribbon-polyaniline nanoribbon composite material is 600-700F/g under the condition that the current density is 0.25A/g, and the specific capacitance retention rate is more than 96% after the graphene nanoribbon-polyaniline nanoribbon composite material is bent for 1000 times. The method is easy to operate and low in cost, and the prepared graphene nanoribbon-polyaniline nanoribbon composite material is large in specific capacitance, good in bending resistance and good in application prospect.
Description
Technical Field
The invention belongs to the field of preparation of nano composite materials, and relates to a graphene nanoribbon-polyaniline nanoribbon composite material and a preparation method thereof.
Background
The graphene-based nanocomposite combines excellent electron/ion transport performance and mechanical property of the graphene material and the properties of electrochemistry and the like of the active nanomaterial, and has wide application value and market prospect in the fields of lithium batteries, supercapacitors and the like. The research on graphene-based nanocomposites in energy storage materials, devices and technologies has been dramatically advancing over the last decade. However, with the development of science and technology and the increase of material culture demand, people have made higher requirements on energy storage materials, such as high reserves, lightness, thinness, flexibility, wearability and the like.
At present, the graphene-based nano composite material is mainly prepared by the following two methods: 1) blending the graphene oxide solution with another nano material, forming a composite material by hydrothermal synthesis, codeposition or in-situ polymerization and other methods, reducing the composite material by chemical reagents or atmosphere reduction and other modes to obtain the graphene-based nano composite material, wherein the formed composite structure is generally in a filling type as shown in figure 1, namely, nano particles, nano spheres or nano rods grow in situ and are filled on the surfaces of graphene sheet layers or among the graphene sheet layers; 2) a network structure is formed firstly by graphene oxide hydrothermal, template impregnation and other methods, then another nano material is wrapped on the surface of the graphene skeleton network by electrochemical deposition, hydrothermal and other methods, and finally the composite structure formed after reduction is called as a 'wrapping' type as shown in fig. 2.
The two methods are simple and universal, but still have problems in conclusion. Firstly, graphene sheets are very easy to stack in the method 1), and the nano material is very easy to agglomerate, so that the nano material is wasted, and the performance of the nano material is reduced. Method 2) can effectively avoid stacking of graphene sheets when forming a composite material, but due to the very large pore structure, the energy storage density per unit volume of the material is low. In addition, both methods have the fatal problem that the nano-materials, whether filled in pores or coated on the surface of the network, basically take the form of nano-particles, when the materials are subjected to external bending deformation, especially multiple times of bending deformation, the nano-particles in the "filled" type structure are easy to agglomerate and shift, and the nano-particles in the "coated" type structure are easy to peel off from the surface of the network, so that the performance of the overall materials is reduced.
Therefore, the development of the graphene-based nanocomposite material capable of effectively avoiding the obvious reduction of material performance caused by bending deformation is of practical significance.
Disclosure of Invention
The invention aims to overcome the defects that the composite material in the prior art is poor in bending deformation resistance and easy to cause performance reduction, and provides a graphene-based nanocomposite material capable of effectively avoiding material performance reduction caused by bending deformation and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a graphene nanoribbon-polyaniline nanoribbon composite material is a composite aerogel which is formed by graphene nanoribbons and polyaniline nanoribbons and has a network interpenetrating structure; after the graphene nanoribbon-polyaniline nanoribbon composite material is bent 1000 times, the specific capacitance retention rate is over 96%. In the prior art, after the graphene-polyaniline nanoparticle composite material is bent for 400 times, the performance of the whole composite material is obviously reduced due to the agglomeration of nanoparticles, the loss of connection between graphene and polyaniline and the like, the specific capacitance of the nanocomposite material is reduced to about 60% of the initial specific capacitance after the graphene-polyaniline nanoparticle composite material is bent for 1000 times, the specific capacitance of the graphene nanoribbon-polyaniline nanoribbon composite material is 600-700F/g under the condition that the current density is 0.25A/g, and the specific capacitance of the existing filled type and coated type graphene-polyaniline nanoparticle composite materials is only 300-450F/g. The prior art cannot simultaneously consider the large specific capacitance and the good bending resistance.
According to the graphene nanoribbon-polyaniline nanoribbon composite material, the conductivity of the graphene nanoribbon-polyaniline nanoribbon composite material is 100-1000S/m, and ions in an electrolyte solution are quickly and effectively transmitted due to the porous structure of the graphene nanoribbon-polyaniline nanoribbon composite material; due to the three-dimensional through of the graphene nanoribbons, excellent conductivity is shown; two types of two-dimensional nano materials are entangled to generate synergistic effects such as a double-network interpenetrating structure and the like, so that the two types of two-dimensional nano materials have more excellent mechanical properties, and the recoverable compressive strain is 10-30%.
According to the graphene nanoribbon-polyaniline nanoribbon composite material, the width of the graphene nanoribbon is 200 nm-1 mu m, the length of the graphene nanoribbon is 3-20 mu m, and the thickness of the graphene nanoribbon is 5-50 nm; the width of the polyaniline nanoribbon is 50-1000 nm, the length of the polyaniline nanoribbon is 10-20 mu m, and the thickness of the polyaniline nanoribbon is 10-100 nm.
The invention also provides a method for preparing the graphene nanoribbon-polyaniline nanoribbon composite material, which comprises the steps of soaking graphene oxide nanoribbon hydrogel in the mixed solution I and the mixed solution II in sequence to obtain the graphene oxide nanoribbon-polyaniline nanoribbon composite material, and reducing to obtain the graphene nanoribbon-polyaniline nanoribbon composite material;
the mixed solution I mainly comprises camphorsulfonic acid, water and aniline, and the mixed solution II mainly comprises ammonium persulfate, water and camphorsulfonic acid or phytic acid.
As a preferred technical scheme:
the method comprises the following steps:
(1) uniformly dispersing carbon nanotubes in concentrated sulfuric acid, keeping a certain stirring speed, sequentially adding phosphoric acid and potassium permanganate, slowly heating to 60-80 ℃, keeping the temperature for 2-3 hours after the temperature is stable, and separating a product to obtain a graphene oxide nanobelt; the temperature is too low, the oxidation reaction is not carried out, and the carbon nano tube is not cut; the temperature is too high, the reaction is too violent, and the nanobelts generate a plurality of defects; the temperature is increased too fast, and the reaction rate is too high, so that the size of the graphene oxide nanoribbon is very uneven; too slow a temperature rise results in too long a whole cycle and the nanobelt size will be small.
(2) Uniformly dispersing the graphene oxide nanoribbon in water, and then adding a surfactant to prepare a graphene oxide nanoribbon stable dispersion liquid; the effect of adding the surfactant is two: (1) the graphene oxide nanoribbon can be uniformly dispersed; (2) the surfactant is dispersed in the solution to play an inducing role in later-stage polyaniline growth into nanobelts, namely a soft template role.
(3) Carrying out hydrothermal reaction on the graphene oxide nanobelt stable dispersion liquid at 120-160 ℃ for 12-36 h to obtain graphene oxide nanobelt hydrogel; when the hydrothermal reaction temperature is lower than 120 ℃, as more oxygen-containing groups exist on the surface of the graphene oxide nanobelt, the graphene oxide nanobelt has stronger electronegativity and hydrophilicity, the coagulation effect of the graphene oxide nanobelt is hindered, and a stable three-dimensional structure cannot be formed; when the temperature is increased from 120 ℃ to 160 ℃, oxygen-containing functional groups are gradually removed, the reduction degree of the graphene oxide nanoribbons is increased, the electrostatic and hydrophilic acting forces are weakened, and the ribbons begin to be interwoven and self-assembled together to form a stable three-dimensional structure; however, with further increase of the hydrothermal temperature, the reduction degree of the graphene oxide nanoribbons is correspondingly increased, the condensation acting force is enhanced, the ribbons are tightly stacked, the agglomeration is serious, and the mesh pore size is reduced. When the hydrothermal reaction time is short, the action of static electricity and hydrogen bonds between the bands is not completely formed under the action of pressure and temperature, and a stable network structure cannot be obtained.
(4) Dissolving camphorsulfonic acid in water, adding aniline to prepare a uniform mixed solution I, and soaking the graphene oxide nanobelt hydrogel into the mixed solution I at room temperature, namely at 15-25 ℃ for 8-24 hours; the permeability rate of the aniline is moderate under the room temperature condition, the gel network structure can be damaged when the temperature is too high, and the permeability rate of the aniline is too low when the temperature is too low; aniline can fully permeate into a porous structure space in the graphene oxide nanobelt hydrogel under the action of the surfactant after soaking for 8-24 hours, the effect cannot be achieved due to too short soaking time, and time and cost are wasted due to too long soaking time.
(5) Dissolving camphorsulfonic acid or phytic acid in water, adding ammonium persulfate to prepare a uniform mixed solution II, soaking the graphene oxide nanobelt hydrogel obtained by the treatment in the step (4) in the mixed solution II, polymerizing for 6-48 hours at 0-4 ℃, washing and drying to obtain the graphene oxide nanobelt-polyaniline nanobelt composite material; the low-temperature (0-4 ℃) polymerization is beneficial to the formation of polyaniline nano-belts, and the excessive high temperature causes the reaction to be too fast, so that the polyaniline nano-rods or nano-particles are formed. When the polymerization time is too short, the polymerization of the polyaniline nanoribbon is insufficient, and when the polymerization time is too long, the formed molecular chain is oxidized and degraded in an oxidizing environment, so that the conductivity of the polyaniline nanoribbon is reduced. The camphorsulfonic acid provides an acidic environment, so that the aniline has good solubility and the conductivity is improved; ammonium persulfate is used as an oxidant, so that aniline can undergo oxidative polymerization at low temperature.
(6) And (3) soaking the graphene oxide nanoribbon-polyaniline nanoribbon composite material in a reducing agent, reacting for 4-12 h at 80-100 ℃, and washing and drying to obtain the graphene nanoribbon-polyaniline nanoribbon composite material. The reduction treatment method can be realized at a lower temperature of less than 100 ℃, the oxygen-containing functional groups of the graphene oxide nanoribbons are removed, simultaneously, reaction products are separated out in a liquid phase form, and the generated capillary force improves the binding force between the graphene nanoribbons, so that the graphene nanoribbons obtained after reduction are remarkably improved in the aspects of conductivity, mechanical strength, flexibility and the like.
According to the method, in the step (1), the mass ratio of the carbon nano tube to the concentrated sulfuric acid to the phosphoric acid to the potassium permanganate is 15-25: 6-10: 1: 75-125; the mass concentration of the concentrated sulfuric acid is 95-98%; the mass concentration of the phosphoric acid is 85 percent; the certain stirring speed is 200-500 rpm; the temperature rising rate of the slow temperature rising is 5-10 ℃/min; and the separation product is sequentially subjected to cooling, standing, cleaning and centrifugal treatment. When the graphene oxide nanoribbon is prepared under the condition of the mass ratio of the oxidant to the carbon nanotube, the oxidation degree of the graphene oxide nanoribbon increases with the increase of the reaction time until saturation is reached. Under the condition of low mass ratio of the oxidant to the carbon nano tube, the oxidant is gradually consumed along with the increase of the reaction time, but when the oxidant is completely consumed or the concentration of the oxidant is very low, the oxygen-containing groups on the surface of the generated graphene oxide nano belt are gradually reduced under the condition of strong acid.
In the method, the cooling and standing refers to that after the mixture is cooled to room temperature, the mixture is poured into ice water containing hydrogen peroxide and stands for 12-24 hours, and the hydrogen peroxide can remove redundant potassium permanganate besides the cooling effect; the cleaning is to use dilute hydrochloric acid to clean the precipitate obtained by cooling and standing for many times; and the centrifugation means that the cleaned precipitate is centrifuged for 2-4 times by using a centrifuge, and the rotating speed of the centrifuge is 8000-10000 rpm.
In the method, in the step (2), the surfactant is sodium dodecyl benzene sulfonate, secondary alkyl sulfonate or fatty acid methyl ester ethoxy compound, and the concentration of the surfactant in the graphene oxide nanobelt stable dispersion liquid is 30-80 mg/mL; the concentration of the graphene oxide nanoribbon in the graphene oxide nanoribbon stable dispersion liquid is 4-10 mg/mL; in the step (4), the mass ratio of the camphorsulfonic acid to the aniline is 2-4: 1; the concentration of aniline in the mixed solution I is 5-25 mg/mL. The acid concentration (2-4: 1) in the mixed solution I is favorable for generating polyaniline with regular structure and higher conductivity; when the acid concentration is lower, polyaniline is formed, meanwhile, phenazine substances and aniline oligomers are generated, the product presents an aggregation structure, and the conductivity of the product is also lower.
According to the method, in the step (5), the mass ratio of the camphor sulfonic acid or the phytic acid to the ammonium persulfate is 4-8: 1; the concentration of ammonium persulfate in the mixed solution II is 8-50 mg/mL; the soaking means that the graphene oxide nanobelt hydrogel is completely immersed in the mixed solution II; in the step (6), the reducing agent is hydroiodic acid, vitamin C, lysine or a mixed solution of vitamin C and lysine, and the mass ratio of the reducing agent to the graphene oxide nanobelt is 3: 1. In the polymerization process, the dosage of the oxidant and the acid concentration are favorable for generating polyaniline with regular structure and higher conductivity; when the using amount of the oxidant is high and the acid concentration is low, polyaniline is formed, meanwhile, the products are in an aggregation structure along with the generation of phenazine substances and aniline oligomers, and the conductivity of the products is also low.
In the method, the washing in the step (5) and the step (6) is washing for 5-6 times by using deionized water and ethanol alternately until the washing solution becomes colorless; the drying in the step (5) and the step (6) is freeze drying or supercritical drying.
The method has the advantages that the drying temperature of the freeze drying is-30 to-40 ℃, and the drying time is 12 to 48 hours; the drying temperature of the supercritical drying is 30-40 ℃, the drying pressure is 8-10 MPa, and the drying time is 4-10 h.
The invention mechanism is as follows:
due to the limitation of the structure of the existing graphene-based nanocomposite, the invention overcomes the problem by preparing the nanobelt to change the material structure.
Compared with nano-structures such as nano-particles and nano-sheets, the nano-belt has the following advantages: 1) the width is large, the contact area of single points among materials and the contact probability among the materials are increased, and the establishment of an electron and ion transmission network is facilitated; 2) the thickness is thin, ions can enter the active material from the thickness direction, and the diffusion distance similar to that of the linear nanometer material is ensured; and more reactive sites due to edge effects; 3) the material has excellent flexibility, can form a good flexible network structure, and can easily keep the flexibility and the bendability of the whole material through the adjustment of the shape of the material when the material is subjected to bending deformation.
Polyaniline is a typical conductive polymer, the main chain of the polymer has a conjugated system, and the polymer can be conductive by doping, and has the advantages of low cost, high conductivity in a doped state, high storage capacity and porosity, wide voltage window, good reversibility, adjustable electrochemical activity and the like. In addition, the polyaniline also has a wide adjustable capacitance range, and can be used for preparing a high-conductivity and high-performance supercapacitor electrode material. However, the conductive polymer has poor conductivity and low electron transfer rate, which limits its use in a supercapacitor. Therefore, the polyaniline is compounded with other high-conductivity carbon materials, so that the method has important significance.
In the invention, a network interpenetrating structure of the graphene nanoribbon and the polyaniline nanoribbon shown in fig. 3 is constructed, and the nano composite material has the following advantages: 1) the porous membrane has three-dimensional communicated pore channels, which is beneficial to the rapid and comprehensive penetration of electrolyte ions, thereby improving effective active sites; 2) the nanobelt has very small thickness, and reduces the ion diffusion distance, thereby improving the material utilization rate; 3) the nanometer material and the graphene nanoribbon are mutually penetrated/wound to form a conductive network, so that the rapid transport of electrons is guaranteed; 4) under the action of external bending stress, the interpenetrating networks formed by the nanobelts have more excellent bending resistance due to the flexibility, mutual sliding and other modes.
Has the advantages that:
(1) the preparation method of the graphene nanoribbon-polyaniline nanoribbon composite material has the advantages of simple preparation process, easiness in operation, ingenious design and high popularization value;
(2) according to the graphene nanoribbon-polyaniline nanoribbon composite material, the graphene nanoribbon is used as a substrate, the high specific surface area is endowed with the unique length-diameter ratio and edge structure of the graphene nanoribbon, and meanwhile, the graphene nanoribbon has excellent conductivity, and electrons and ions can be quickly and effectively transmitted in an electrocatalysis process due to the lamellar structure of the graphene nanoribbon; the compounding of the quasi-one-dimensional material and the two-dimensional material is realized by a hydrothermal method, so that the advantages of the two materials are fully exerted, and the composite material with excellent performance is constructed;
(3) the graphene nanoribbon-polyaniline nanoribbon composite material can be used as a high-performance supercapacitor electrode material and an ideal electrode material for novel energy sources such as lithium ion batteries and solar batteries, and has a wide application prospect.
Drawings
FIG. 1 is a schematic structural diagram of a "filled" composite-structure graphene-based nanocomposite;
FIG. 2 is a schematic structural view of a graphene-based nanocomposite material with a "clad" composite structure;
FIG. 3 is a schematic structural diagram of a graphene nanoribbon-polyaniline nanoribbon composite of the present invention;
FIG. 4 is a schematic diagram of bending test of graphene/polyaniline nanocomposite;
fig. 5 is a comparison graph of the effect of bending on the specific capacitance of a graphene/polyaniline nanoribbon composite (a is the graphene nanoribbon-polyaniline nanoribbon composite of the present invention, and B is graphene/polyaniline nanoparticles);
the nano-material comprises 1-graphene, 2-filling nano-materials, 3-wrapping nano-materials, 4-graphene frameworks, 5-polyaniline nanobelts and 6-graphene nanobelts.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of a graphene nanoribbon-polyaniline nanoribbon composite material comprises the following preparation steps:
(1) uniformly dispersing carbon nanotubes in concentrated sulfuric acid, keeping the stirring speed of 300rpm, sequentially adding phosphoric acid and potassium permanganate, slowly heating to 70 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours after the temperature is stabilized, cooling to room temperature, pouring into ice water containing hydrogen peroxide, standing for 12 hours, washing the precipitate obtained by cooling and standing for many times by using dilute hydrochloric acid, and centrifuging the washed precipitate for 2 times to obtain the graphene oxide nanobelt, wherein the mass ratio of the carbon nanotubes to the concentrated sulfuric acid to the phosphoric acid to the potassium permanganate is 15:6:1:75, the mass concentration of the concentrated sulfuric acid is 98%, the mass concentration of the phosphoric acid is 85%, and the rotation speed of a centrifuge is 9000 rpm;
(2) uniformly dispersing the graphene oxide nanoribbons in water, and then adding sodium dodecyl benzene sulfonate to prepare a graphene oxide nanoribbon stable dispersion liquid, wherein the concentration of the graphene oxide nanoribbons in the graphene oxide nanoribbon stable dispersion liquid is 4mg/mL, and the concentration of the sodium dodecyl benzene sulfonate is 50 mg/mL;
(3) carrying out hydrothermal reaction on the graphene oxide nanobelt stable dispersion liquid for 14h at 120 ℃ to obtain graphene oxide nanobelt hydrogel;
(4) dissolving camphorsulfonic acid in water, adding aniline to prepare a uniform mixed solution I, and soaking graphene oxide nanobelt hydrogel into the mixed solution I at 20 ℃ for 16 hours, wherein the mass ratio of the camphorsulfonic acid to the aniline is 3:1, and the concentration of the aniline in the mixed solution I is 15 mg/mL;
(5) dissolving camphorsulfonic acid in water, adding ammonium persulfate to prepare a uniform mixed solution II, completely immersing the graphene oxide nanobelt hydrogel obtained by the treatment in the step (4) in the mixed solution II, polymerizing at 2 ℃ for 24 hours, alternately washing with deionized water and ethanol for 6 times until the washing solution becomes colorless, and freeze-drying to obtain the graphene oxide nanobelt-polyaniline nanobelt composite material, wherein the mass ratio of the camphorsulfonic acid to the ammonium persulfate is 5:1, the concentration of the ammonium persulfate in the mixed solution II is 20mg/mL, the drying temperature of freeze-drying is-35 ℃, and the drying time is 40 hours;
(6) the graphene oxide nanoribbon-polyaniline nanoribbon composite material is soaked in hydroiodic acid to react for 8 hours at 90 ℃, then deionized water and ethanol are used for alternately washing for 6 times until the washing solution becomes colorless, and the graphene oxide nanoribbon-polyaniline nanoribbon composite material is obtained after freeze drying, wherein the mass ratio of the hydroiodic acid to the graphene oxide nanoribbon is 3:1, the drying temperature of the freeze drying is-35 ℃, and the drying time is 30 hours.
The finally prepared graphene nanoribbon-polyaniline nanoribbon composite material is composite aerogel which is formed by graphene nanoribbons and polyaniline nanoribbons and has a network interpenetrating structure, the width of each graphene nanoribbon is 600nm, the length of each graphene nanoribbon is 12 micrometers, the thickness of each graphene nanoribbon is 45nm, the width of each polyaniline nanoribbon is 500nm, the length of each polyaniline nanoribbon is 15 micrometers, the thickness of each polyaniline nanoribbon is 50nm, the conductivity of the prepared graphene nanoribbon-polyaniline nanoribbon composite material is 900S/m, the recoverable compression strain is 28%, and the specific capacitance is 700F/g under the condition that the current density is 0.25A/g.
The specific capacitance (F/g) of the material is obtained through a cyclic voltammetry test by an electrochemical workstation, after the material is bent for multiple times according to the method shown in FIG. 4 (the sample is fixed on a substrate by a clamp and bent by 150 degrees according to a dotted line), the specific capacitance of the material is retested, the influence of the bending on the specific capacitance performance of the graphene nanoribbon/polyaniline nanoribbon composite material is represented, and the specific capacitance retention rate of the graphene nanoribbon/polyaniline nanoribbon composite material is measured to be 96%.
Comparative example 1
A preparation method of a graphene-polyaniline nanoparticle composite material is characterized in that a filled graphene-polyaniline nanoparticle composite material is prepared by in-situ polymerization of a graphene oxide solution and aniline. The bending test of the prepared graphene-polyaniline nanoparticle composite material is the same as that of the embodiment 1, the specific capacitance change curve of the graphene nanoribbon-polyaniline nanoribbon composite material prepared in the embodiment 1 and the graphene-polyaniline nanoparticle composite material prepared in the comparative example 1 is shown in fig. 5, wherein a is the graphene nanoribbon-polyaniline nanoribbon composite material of the invention, and B is the graphene-polyaniline nanoparticle composite material, and as can be seen from fig. 5, after the graphene nanoribbon-polyaniline nanoribbon composite material is bent for 1000 times, the specific capacitance retention rate of the graphene nanoribbon-polyaniline nanoribbon composite material of the invention is still about 96%; after the graphene/polyaniline nanoparticle composite material is bent for 400 times, the performance of the whole composite material is obviously reduced due to the agglomeration of polyaniline nanoparticles, the separation of polyaniline and graphene and the like, the specific capacitance of the nanocomposite material is reduced to about 60% of the initial specific capacitance after the graphene/polyaniline nanoparticle composite material is bent for 1000 times, and the specific capacitance is 330F/g under the condition that the current density is 0.25A/g. The graphene nanoribbon-polyaniline nanoribbon composite material prepared by the method has excellent bending deformation resistance, and is remarkably improved compared with the prior art.
Comparative example 2
A preparation method of a carbon nanotube-polyaniline nanoribbon composite material comprises the following steps:
(1) adding sodium dodecyl benzene sulfonate into water, wherein the concentration of the sodium dodecyl benzene sulfonate is 50mg/mL, then adding the single-walled carbon nanotube, and preparing a stable dispersion liquid of the carbon nanotube after ultrasonic dispersion for 4 hours, wherein the concentration of the single-walled carbon nanotube is 8 mg/mL;
(2) continuously carrying out ultrasonic dispersion on the single-walled carbon nanotube solution for 16h to obtain single-walled carbon nanotube gel;
(3) dissolving camphorsulfonic acid in water, adding aniline to prepare a uniform mixed solution I, and then soaking the carbon nano tube hydrogel into the mixed solution I at the temperature of 20 ℃ for 16 hours, wherein the mass ratio of the camphorsulfonic acid to the aniline is 3:1, and the concentration of the aniline in the mixed solution I is 15 mg/mL;
(4) dissolving camphorsulfonic acid in water, adding ammonium persulfate to prepare uniform mixed solution II, completely immersing the carbon nano tube hydrogel obtained by the treatment in the step (3) in the mixed solution II, polymerizing at 2 ℃ for 24h, alternately washing with deionized water and ethanol for 6 times until the washing solution becomes colorless, and freeze-drying to obtain the carbon nano tube-polyaniline nano belt composite material, wherein the mass ratio of the camphorsulfonic acid to the ammonium persulfate is 5:1, the concentration of the ammonium persulfate in the mixed solution II is 20mg/mL, the drying temperature of freeze-drying is-35 ℃, and the drying time is 40 h.
The polyaniline nanoribbon and the carbon nanotube in the finally prepared carbon nanotube-polyaniline nanoribbon composite material form a network interpenetrating structure, the specific capacitance of the carbon nanotube-polyaniline nanoribbon composite material is 450F/g under the condition that the current density is 0.25A/g, and after bending for 1000 times, the specific capacitance retention rate is 94%, and compared with example 1, the bending resistance of the carbon nanotube-polyaniline nanoribbon composite material is almost the same, and the excellent bending resistance of the carbon nanotube-polyaniline nanoribbon composite material is derived from the network interpenetrating structure. However, the specific capacitance of the graphene nanoribbon-polyaniline nanoribbon in the invention can reach 700F/g, which is much better than that of the carbon nanotube-polyaniline nanoribbon composite material, because the graphene nanoribbon has larger size and larger space in a formed network structure compared with the carbon nanotube, which is more beneficial to the growth of the polyaniline nanoribbon, the polyaniline content in the composite material is higher, and the specific capacitance of the final composite material is higher.
Example 2
A preparation method of a graphene nanoribbon-polyaniline nanoribbon composite material comprises the following preparation steps:
(1) uniformly dispersing carbon nanotubes in concentrated sulfuric acid, keeping a stirring speed of 200rpm, sequentially adding phosphoric acid and potassium permanganate, slowly heating to 60 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 2 hours after the temperature is stabilized, cooling to room temperature, pouring into ice water containing hydrogen peroxide, standing for 12 hours, washing the precipitate obtained by cooling and standing for many times by using dilute hydrochloric acid, and centrifuging the washed precipitate for 2 times to obtain the graphene oxide nanobelt, wherein the mass ratio of the carbon nanotubes to the concentrated sulfuric acid to the phosphoric acid to the potassium permanganate is 15:6:1:75, the mass concentration of the concentrated sulfuric acid is 95%, the mass concentration of the phosphoric acid is 85%, and the rotation speed of a centrifuge is 8000 rpm;
(2) uniformly dispersing graphene oxide nanoribbons in water, and then adding secondary sodium alkylsulfonate to prepare a graphene oxide nanoribbon stable dispersion liquid, wherein the concentration of the graphene oxide nanoribbons in the graphene oxide nanoribbon stable dispersion liquid is 4mg/mL, and the concentration of the secondary sodium alkylsulfonate is 30 mg/mL;
(3) carrying out hydrothermal reaction on the graphene oxide nanobelt stable dispersion liquid at 120 ℃ for 12h to obtain graphene oxide nanobelt hydrogel;
(4) dissolving camphorsulfonic acid in water, adding aniline to prepare a uniform mixed solution I, and soaking graphene oxide nanobelt hydrogel into the mixed solution I at 15 ℃ for 8 hours, wherein the mass ratio of the camphorsulfonic acid to the aniline is 2:1, and the concentration of the aniline in the mixed solution I is 5 mg/mL;
(5) dissolving phytic acid in water, adding ammonium persulfate to prepare a uniform mixed solution II, completely immersing the graphene oxide nanobelt hydrogel obtained by the treatment in the step (4) in the mixed solution II, polymerizing for 6 hours at 0 ℃, alternately washing for 6 times by using deionized water and ethanol until the washing solution becomes colorless, and freeze-drying to obtain the graphene oxide nanobelt-polyaniline nanobelt composite material, wherein the mass ratio of the phytic acid to the ammonium persulfate is 4:1, the concentration of the ammonium persulfate in the mixed solution II is 8mg/mL, the freeze-drying temperature is-30 ℃, and the drying time is 48 hours;
(6) the graphene oxide nanoribbon-polyaniline nanoribbon composite material is soaked in vitamin C to react for 8 hours at 80 ℃, then deionized water and ethanol are used for alternately washing for 6 times until a washing solution becomes colorless, and the graphene oxide nanoribbon-polyaniline nanoribbon composite material is obtained after freeze drying, wherein the mass ratio of the vitamin C to the graphene oxide nanoribbon is 3:1, the drying temperature of the freeze drying is-30 ℃, and the drying time is 48 hours.
The finally prepared graphene nanoribbon-polyaniline nanoribbon composite material is a composite aerogel which is formed by graphene nanoribbons and polyaniline nanoribbons and has a network interpenetrating structure, the width of each graphene nanoribbon is 200nm, the length of each graphene nanoribbon is 20 microns, the thickness of each graphene nanoribbon is 50nm, the width of each polyaniline nanoribbon is 1000nm, the length of each polyaniline nanoribbon is 20 microns, the thickness of each polyaniline nanoribbon is 100nm, the conductivity of the prepared graphene nanoribbon-polyaniline nanoribbon composite material is 100S/m, the recoverable compression strain is 10%, the specific capacitance of the graphene nanoribbon-polyaniline nanoribbon composite material is 600F/g under the condition that the current density is 0.25A/g, and the specific capacitance retention rate of the graphene nanoribbon-polyaniline nanoribbon composite material after being bent for 1000 times is 96.2%.
Example 3
A preparation method of a graphene nanoribbon-polyaniline nanoribbon composite material comprises the following preparation steps:
(1) uniformly dispersing carbon nanotubes in concentrated sulfuric acid, keeping the stirring speed of 500rpm, sequentially adding phosphoric acid and potassium permanganate, slowly heating to 80 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 3 hours after the temperature is stabilized, cooling to room temperature, pouring into ice water containing hydrogen peroxide, standing for 24 hours, washing the precipitate obtained by cooling and standing for many times by using dilute hydrochloric acid, and centrifuging the washed precipitate for 4 times to obtain the graphene oxide nanobelt, wherein the mass ratio of the carbon nanotubes to the concentrated sulfuric acid to the phosphoric acid to the potassium permanganate is 25:10:1:125, the mass concentration of the concentrated sulfuric acid is 98%, the mass concentration of the phosphoric acid is 85%, and the rotation speed of a centrifuge is 10000 rpm;
(2) uniformly dispersing the graphene oxide nanoribbons in water, and then adding sodium methyl stearate polyoxyethylene ether sulfonate to prepare a stable graphene oxide nanoribbon dispersion liquid, wherein the concentration of the graphene oxide nanoribbons in the stable graphene oxide nanoribbon dispersion liquid is 10mg/mL, and the concentration of the sodium methyl stearate polyoxyethylene ether sulfonate is 80 mg/mL;
(3) carrying out hydrothermal reaction on the graphene oxide nanobelt stable dispersion liquid for 36 hours at 160 ℃ to obtain graphene oxide nanobelt hydrogel;
(4) dissolving camphorsulfonic acid in water, adding aniline to prepare a uniform mixed solution I, and soaking graphene oxide nanobelt hydrogel into the mixed solution I at 25 ℃ for 24 hours, wherein the mass ratio of the camphorsulfonic acid to the aniline is 4:1, and the concentration of the aniline in the mixed solution I is 25 mg/mL;
(5) dissolving camphorsulfonic acid in water, adding ammonium persulfate to prepare a uniform mixed solution II, completely immersing the graphene oxide nanobelt hydrogel obtained by the treatment in the step (4) in the mixed solution II, polymerizing for 48 hours at 4 ℃, alternately washing for 5 times by using deionized water and ethanol until the washing solution becomes colorless, and freeze-drying to obtain the graphene oxide nanobelt-polyaniline nanobelt composite material, wherein the mass ratio of the camphorsulfonic acid to the ammonium persulfate is 8:1, the concentration of the ammonium persulfate in the mixed solution II is 50mg/mL, the drying temperature of freeze-drying is-40 ℃, and the drying time is 12 hours;
(6) the graphene oxide nanoribbon-polyaniline nanoribbon composite material is soaked in lysine to react for 12 hours at 100 ℃, then deionized water and ethanol are used for alternately washing for 5 times until a washing solution becomes colorless, and the graphene oxide nanoribbon-polyaniline nanoribbon composite material is obtained after freeze drying, wherein the mass ratio of lysine to graphene oxide nanoribbon is 3:1, the drying temperature of freeze drying is-40 ℃, and the drying time is 12 hours.
The finally prepared graphene nanoribbon-polyaniline nanoribbon composite material is a composite aerogel which is formed by graphene nanoribbons and polyaniline nanoribbons and has a network interpenetrating structure, the width of each graphene nanoribbon is 1 mu m, the length of each graphene nanoribbon is 3 mu m, the thickness of each graphene nanoribbon is 5nm, the width of each polyaniline nanoribbon is 50nm, the length of each polyaniline nanoribbon is 10 mu m, the thickness of each polyaniline nanoribbon is 10nm, the conductivity of the prepared graphene nanoribbon-polyaniline nanoribbon composite material is 120S/m, the recoverable compressive strain is 15%, the specific capacitance of the graphene nanoribbon-polyaniline nanoribbon composite material is 650F/g under the condition that the current density is 0.25A/g, and the specific capacitance retention rate of the graphene nanoribbon-polyaniline nanoribbon composite material after being bent for 1000 times is 96.5%.
Example 4
A preparation method of a graphene nanoribbon-polyaniline nanoribbon composite material comprises the following preparation steps:
(1) uniformly dispersing carbon nanotubes in concentrated sulfuric acid, keeping the stirring speed of 300rpm, sequentially adding phosphoric acid and potassium permanganate, slowly heating to 65 ℃ at the heating rate of 7 ℃/min, keeping the temperature for 2 hours after the temperature is stabilized, cooling to room temperature, pouring into ice water containing hydrogen peroxide, standing for 16 hours, washing the precipitate obtained by cooling and standing for many times by using dilute hydrochloric acid, and centrifuging the washed precipitate for 3 times to obtain the graphene oxide nanobelt, wherein the mass ratio of the carbon nanotubes to the concentrated sulfuric acid to the phosphoric acid to the potassium permanganate is 18:8:1:80, the mass concentration of the concentrated sulfuric acid is 96%, the mass concentration of the phosphoric acid is 85%, and the rotation speed of a centrifuge is 8500 rpm;
(2) uniformly dispersing the graphene oxide nanoribbons in water, and then adding sodium dodecyl benzene sulfonate to prepare a graphene oxide nanoribbon stable dispersion liquid, wherein the concentration of the graphene oxide nanoribbons in the graphene oxide nanoribbon stable dispersion liquid is 5mg/mL, and the concentration of the sodium dodecyl benzene sulfonate is 40 mg/mL;
(3) carrying out hydrothermal reaction on the graphene oxide nanobelt stable dispersion liquid for 18h at 140 ℃ to obtain graphene oxide nanobelt hydrogel;
(4) dissolving camphorsulfonic acid in water, adding aniline to prepare a uniform mixed solution I, and soaking graphene oxide nanobelt hydrogel into the mixed solution I at 20 ℃ for 20 hours, wherein the mass ratio of the camphorsulfonic acid to the aniline is 2:1, and the concentration of the aniline in the mixed solution I is 20 mg/mL;
(5) dissolving camphorsulfonic acid in water, adding ammonium persulfate to prepare a uniform mixed solution II, completely immersing the graphene oxide nanobelt hydrogel obtained by the treatment in the step (4) in the mixed solution II, polymerizing for 8 hours at 0 ℃, alternately washing for 6 times by using deionized water and ethanol until the washing solution becomes colorless, and freeze-drying to obtain the graphene oxide nanobelt-polyaniline nanobelt composite material, wherein the mass ratio of the camphorsulfonic acid to the ammonium persulfate is 6:1, the concentration of the ammonium persulfate in the mixed solution II is 15mg/mL, the drying temperature of freeze-drying is-35 ℃, and the drying time is 20 hours;
(6) the graphene oxide nanoribbon-polyaniline nanoribbon composite material is firstly soaked in a mixed solution (mass ratio is 1:1) of vitamin C and lysine to react for 6 hours at 90 ℃, then deionized water and ethanol are used for alternately washing for 6 times until the washing solution becomes colorless, and the graphene oxide nanoribbon-polyaniline nanoribbon composite material is obtained after freeze drying, wherein the mass ratio of the mixed solution of the vitamin C and the lysine to the graphene oxide nanoribbon is 3:1, the drying temperature of freeze drying is-35 ℃, and the drying time is 20 hours.
The finally prepared graphene nanoribbon-polyaniline nanoribbon composite material is a composite aerogel which is formed by graphene nanoribbons and polyaniline nanoribbons and has a network interpenetrating structure, the width of each graphene nanoribbon is 400nm, the length of each graphene nanoribbon is 10 microns, the thickness of each graphene nanoribbon is 20nm, the width of each polyaniline nanoribbon is 200nm, the length of each polyaniline nanoribbon is 15 microns, the thickness of each polyaniline nanoribbon is 30nm, the conductivity of the prepared graphene nanoribbon-polyaniline nanoribbon composite material is 400S/m, the recoverable compression strain is 20%, the specific capacitance of the graphene nanoribbon-polyaniline nanoribbon composite material is 680F/g under the condition that the current density is 0.25A/g, and the specific capacitance retention rate of the graphene nanoribbon-polyaniline nanoribbon composite material after being bent for 1000 times is 97%.
Example 5
A preparation method of a graphene nanoribbon-polyaniline nanoribbon composite material comprises the following preparation steps:
(1) uniformly dispersing carbon nanotubes in concentrated sulfuric acid, keeping a stirring speed of 400rpm, sequentially adding phosphoric acid and potassium permanganate, slowly heating to 70 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 3 hours after the temperature is stabilized, cooling to room temperature, pouring into ice water containing hydrogen peroxide, standing for 20 hours, washing the precipitate obtained by cooling and standing for many times by using dilute hydrochloric acid, and centrifuging the washed precipitate for 2 times to obtain the graphene oxide nanobelt, wherein the mass ratio of the carbon nanotubes to the concentrated sulfuric acid to the phosphoric acid to the potassium permanganate is 20:10:1:120, the mass concentration of the concentrated sulfuric acid is 97%, the mass concentration of the phosphoric acid is 85%, and the rotation speed of a centrifuge is 9000 rpm;
(2) uniformly dispersing the graphene oxide nanoribbons in water, and then adding sodium dodecyl benzene sulfonate to prepare a graphene oxide nanoribbon stable dispersion liquid, wherein the concentration of the graphene oxide nanoribbons in the graphene oxide nanoribbon stable dispersion liquid is 8mg/mL, and the concentration of the sodium dodecyl benzene sulfonate is 60 mg/mL;
(3) carrying out hydrothermal reaction on the graphene oxide nanobelt stable dispersion liquid for 25h at 150 ℃ to obtain graphene oxide nanobelt hydrogel;
(4) dissolving camphorsulfonic acid in water, adding aniline to prepare a uniform mixed solution I, and soaking graphene oxide nanobelt hydrogel into the mixed solution I at 25 ℃ for 24 hours, wherein the mass ratio of the camphorsulfonic acid to the aniline is 4:1, and the concentration of the aniline in the mixed solution I is 20 mg/mL;
(5) dissolving camphorsulfonic acid in water, adding ammonium persulfate to prepare a uniform mixed solution II, completely immersing the graphene oxide nanobelt hydrogel obtained by the treatment in the step (4) in the mixed solution II, polymerizing for 6 hours at 0 ℃, alternately washing for 5 times by using deionized water and ethanol until the washing solution becomes colorless, and performing supercritical drying to obtain the graphene oxide nanobelt-polyaniline nanobelt composite material, wherein the mass ratio of the camphorsulfonic acid to the ammonium persulfate is 7:1, the concentration of the ammonium persulfate in the mixed solution II is 30mg/mL, the drying temperature of the supercritical drying is 40 ℃, the drying pressure is 10MPa, and the drying time is 10 hours;
(6) the graphene oxide nanoribbon-polyaniline nanoribbon composite material is soaked in hydroiodic acid to react for 10 hours at the temperature of 80 ℃, then deionized water and ethanol are used for alternately washing for 5 times until the washing solution becomes colorless, and the graphene oxide nanoribbon-polyaniline nanoribbon composite material is obtained after supercritical drying, wherein the mass ratio of the hydroiodic acid to the graphene oxide nanoribbon is 3:1, the drying temperature of the supercritical drying is 40 ℃, the drying pressure is 10MPa, and the drying time is 10 hours.
The finally prepared graphene nanoribbon-polyaniline nanoribbon composite material is a composite aerogel which is formed by graphene nanoribbons and polyaniline nanoribbons and has a network interpenetrating structure, the width of each graphene nanoribbon is 800nm, the length of each graphene nanoribbon is 10 microns, the thickness of each graphene nanoribbon is 40nm, the width of each polyaniline nanoribbon is 700nm, the length of each polyaniline nanoribbon is 20 microns, the thickness of each polyaniline nanoribbon is 80nm, the conductivity of the prepared graphene nanoribbon-polyaniline nanoribbon composite material is 900S/m, the recoverable compressive strain is 25%, the specific capacitance of the composite material is 640F/g under the condition that the current density is 0.25A/g, and the specific capacitance retention rate of the graphene nanoribbon-polyaniline nanoribbon composite material after being bent for 1000 times is 96.7%.
Example 6
A preparation method of a graphene nanoribbon-polyaniline nanoribbon composite material comprises the following preparation steps:
(1) uniformly dispersing carbon nanotubes in concentrated sulfuric acid, keeping the stirring speed of 500rpm, sequentially adding phosphoric acid and potassium permanganate, slowly heating to 60 ℃ at the heating rate of 8 ℃/min, keeping the temperature for 3 hours after the temperature is stabilized, cooling to room temperature, pouring into ice water containing hydrogen peroxide, standing for 20 hours, washing the precipitate obtained by cooling and standing for many times by using dilute hydrochloric acid, and centrifuging the washed precipitate for 4 times to obtain the graphene oxide nanobelt, wherein the mass ratio of the carbon nanotubes to the concentrated sulfuric acid to the phosphoric acid to the potassium permanganate is 25:6:1:100, the mass concentration of the concentrated sulfuric acid is 95%, the mass concentration of the phosphoric acid is 85%, and the rotation speed of a centrifuge is 9500 rpm;
(2) uniformly dispersing graphene oxide nanoribbons in water, and then adding secondary sodium alkylsulfonate to prepare a graphene oxide nanoribbon stable dispersion liquid, wherein the concentration of the graphene oxide nanoribbons in the graphene oxide nanoribbon stable dispersion liquid is 10mg/mL, and the concentration of the secondary sodium alkylsulfonate is 50 mg/mL;
(3) carrying out hydrothermal reaction on the graphene oxide nanobelt stable dispersion liquid for 36 hours at 160 ℃ to obtain graphene oxide nanobelt hydrogel;
(4) dissolving camphorsulfonic acid in water, adding aniline to prepare a uniform mixed solution I, and soaking graphene oxide nanobelt hydrogel into the mixed solution I at 20 ℃ for 20 hours, wherein the mass ratio of the camphorsulfonic acid to the aniline is 4:1, and the concentration of the aniline in the mixed solution I is 20 mg/mL;
(5) dissolving camphorsulfonic acid in water, adding ammonium persulfate to prepare a uniform mixed solution II, completely immersing the graphene oxide nanobelt hydrogel obtained by the treatment in the step (4) in the mixed solution II, polymerizing at 3 ℃ for 18h, alternately washing with deionized water and ethanol for 6 times until the washing solution becomes colorless, and performing supercritical drying to obtain the graphene oxide nanobelt-polyaniline nanobelt composite material, wherein the mass ratio of the camphorsulfonic acid to the ammonium persulfate is 5:1, the concentration of the ammonium persulfate in the mixed solution II is 40mg/mL, the drying temperature of the supercritical drying is 30 ℃, the drying pressure is 8MPa, and the drying time is 4 h;
(6) the graphene oxide nanoribbon-polyaniline nanoribbon composite material is soaked in vitamin C to react for 10 hours at 85 ℃, then deionized water and ethanol are used for alternately washing for 6 times until a washing solution becomes colorless, and the graphene oxide nanoribbon-polyaniline nanoribbon composite material is obtained after supercritical drying, wherein the mass ratio of the vitamin C to the graphene oxide nanoribbon is 3:1, the drying temperature of the supercritical drying is 30 ℃, the drying pressure is 8MPa, and the drying time is 4 hours.
The finally prepared graphene nanoribbon-polyaniline nanoribbon composite material is a composite aerogel which is formed by graphene nanoribbons and polyaniline nanoribbons and has a network interpenetrating structure, the width of each graphene nanoribbon is 1 mu m, the length of each graphene nanoribbon is 20 mu m, the thickness of each graphene nanoribbon is 40nm, the width of each polyaniline nanoribbon is 700nm, the length of each polyaniline nanoribbon is 15 mu m, the thickness of each polyaniline nanoribbon is 80nm, the conductivity of the prepared graphene nanoribbon-polyaniline nanoribbon composite material is 950S/m, the recoverable compressive strain is 25%, the specific capacitance of the graphene nanoribbon-polyaniline nanoribbon composite material is 630F/g under the condition that the current density is 0.25A/g, and the specific capacitance retention rate of the graphene nanoribbon-polyaniline nanoribbon composite material after being bent for 1000 times is 97.2%.
Claims (9)
1. A preparation method of a graphene nanoribbon-polyaniline nanoribbon composite material is characterized by comprising the following specific steps:
(1) uniformly dispersing carbon nanotubes in sulfuric acid with the mass concentration of 95-98%, keeping a certain stirring speed, sequentially adding phosphoric acid and potassium permanganate, slowly heating to 60-80 ℃, keeping the temperature for 2-3 hours after the temperature is stable, and separating a product to obtain a graphene oxide nanobelt;
(2) uniformly dispersing the graphene oxide nanoribbon in water, and then adding a surfactant to prepare a graphene oxide nanoribbon stable dispersion liquid;
(3) carrying out hydrothermal reaction on the graphene oxide nanobelt stable dispersion liquid at 120-160 ℃ for 12-36 h to obtain graphene oxide nanobelt hydrogel;
(4) dissolving camphorsulfonic acid in water, adding aniline to prepare a uniform mixed solution I, and soaking graphene oxide nanobelt hydrogel into the mixed solution I at 15-25 ℃ for 8-24 hours;
(5) dissolving camphorsulfonic acid or phytic acid in water, adding ammonium persulfate to prepare a uniform mixed solution II, soaking the graphene oxide nanobelt hydrogel obtained by the treatment in the step (4) in the mixed solution II, polymerizing for 6-48 hours at 0-4 ℃, washing and drying to obtain the graphene oxide nanobelt-polyaniline nanobelt composite material;
(6) and (3) dipping the graphene oxide nanoribbon-polyaniline nanoribbon composite material in a reducing agent, reacting for 4-12 h at 80-100 ℃, and washing and drying to obtain the graphene nanoribbon-polyaniline nanoribbon composite material.
2. The preparation method of the graphene nanoribbon-polyaniline nanoribbon composite material according to claim 1, wherein in the step (1), the mass ratio of the carbon nanotubes to sulfuric acid to phosphoric acid to potassium permanganate is 15-25: 6-10: 1: 75-125; the mass concentration of the phosphoric acid is 85 percent; the certain stirring speed is 200-500 rpm; the temperature rising rate of the slow temperature rising is 5-10 ℃/min; and the separation product is sequentially subjected to cooling, standing, cleaning and centrifugal treatment.
3. The preparation method of the graphene nanoribbon-polyaniline nanoribbon composite material as claimed in claim 2, wherein the cooling and standing is that the graphene nanoribbon-polyaniline nanoribbon composite material is cooled to room temperature, poured into ice water containing hydrogen peroxide and kept standing for 12-24 hours; the cleaning is to use hydrochloric acid to clean the precipitate obtained by cooling and standing for many times; and the centrifugation means that the cleaned precipitate is centrifuged for 2-4 times by using a centrifuge, and the rotating speed of the centrifuge is 8000-10000 rpm.
4. The method for preparing the graphene nanoribbon-polyaniline nanoribbon composite material as claimed in claim 1, wherein in the step (2), the surfactant is sodium dodecyl benzene sulfonate, secondary alkyl sodium sulfonate or fatty acid methyl ester ethoxy compound, and the concentration of the surfactant in the graphene oxide nanoribbon stable dispersion liquid is 30-80 mg/mL; the concentration of the graphene oxide nanoribbon in the graphene oxide nanoribbon stable dispersion liquid is 4-10 mg/mL; in the step (4), the mass ratio of the camphorsulfonic acid to the aniline is 2-4: 1; the concentration of aniline in the mixed solution I is 5-25 mg/mL; in the step (5), the mass ratio of the camphorsulfonic acid or phytic acid to the ammonium persulfate is 4-8: 1; the concentration of ammonium persulfate in the mixed solution II is 8-50 mg/mL; the soaking means that the graphene oxide nanobelt hydrogel is completely immersed in the mixed solution II; in the step (6), the reducing agent is hydroiodic acid, vitamin C, lysine or a mixed solution of vitamin C and lysine, and the mass ratio of the reducing agent to the graphene oxide nanobelt is 3: 1.
5. The preparation method of the graphene nanoribbon-polyaniline nanoribbon composite material as claimed in claim 1, wherein the washing in the steps (5) and (6) is performed by alternately washing with deionized water and ethanol for 5-6 times until the washing solution becomes colorless; the drying in the step (5) and the step (6) is freeze drying or supercritical drying.
6. The preparation method of the graphene nanoribbon-polyaniline nanoribbon composite material as claimed in claim 5, wherein the freeze drying is carried out at a drying temperature of-30 to-40 ℃ for 12 to 48 hours; the drying temperature of the supercritical drying is 30-40 ℃, the drying pressure is 8-10 MPa, and the drying time is 4-10 h.
7. A graphene nanoribbon-polyaniline nanoribbon composite material prepared by the method for preparing the graphene nanoribbon-polyaniline nanoribbon composite material as described in any one of claims 1 to 6, which is characterized in that: the graphene nanoribbon-polyaniline nanoribbon composite material is composite aerogel which is formed by graphene nanoribbons and polyaniline nanoribbons and has a network interpenetrating structure; after the graphene nanoribbon-polyaniline nanoribbon composite material is bent for 1000 times, the specific capacitance retention rate is over 96%, and the specific capacitance of the graphene nanoribbon-polyaniline nanoribbon composite material is 600-700F/g under the condition that the current density is 0.25A/g.
8. The graphene nanoribbon-polyaniline nanoribbon composite material as claimed in claim 7, wherein the graphene nanoribbon-polyaniline nanoribbon composite material has an electrical conductivity of 100-1000S/m and a recoverable compressive strain of 10-30%.
9. The graphene nanoribbon-polyaniline nanoribbon composite material as claimed in claim 7, wherein the graphene nanoribbon has a width of 200nm to 1 μm, a length of 3 to 20 μm, and a thickness of 5 to 50 nm; the width of the polyaniline nanoribbon is 50-1000 nm, the length of the polyaniline nanoribbon is 10-20 mu m, and the thickness of the polyaniline nanoribbon is 10-100 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810435311.9A CN108570229B (en) | 2018-05-09 | 2018-05-09 | Graphene nanoribbon-polyaniline nanoribbon composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810435311.9A CN108570229B (en) | 2018-05-09 | 2018-05-09 | Graphene nanoribbon-polyaniline nanoribbon composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108570229A CN108570229A (en) | 2018-09-25 |
| CN108570229B true CN108570229B (en) | 2020-08-14 |
Family
ID=63571940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810435311.9A Active CN108570229B (en) | 2018-05-09 | 2018-05-09 | Graphene nanoribbon-polyaniline nanoribbon composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108570229B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110534353B (en) * | 2019-09-19 | 2020-11-03 | 福州大学 | Preparation method and application of poly (3, 4-ethylenedioxythiophene) composite material |
| CN111484644A (en) * | 2020-04-17 | 2020-08-04 | 东华理工大学 | Method for preparing, separating and enriching uranium from polyamidoxime/graphene nanoribbon composite aerogel |
| CN114752075B (en) * | 2022-03-08 | 2024-03-22 | 武汉工程大学 | Preparation method of copper sulfide-graphene-polyaniline composite hydrogel |
| CN115863062B (en) * | 2022-12-27 | 2023-07-28 | 武汉立承科技有限公司 | Graphene nanobelt/metal oxide nanobelt composite film and preparation and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201012749A (en) * | 2008-08-19 | 2010-04-01 | Univ Rice William M | Methods for preparation of graphene nanoribbons from carbon nanotubes and compositions, thin films and devices derived therefrom |
| CN104817075B (en) * | 2015-04-17 | 2021-04-13 | 重庆大学 | Preparation method of highly dispersed graphene oxide nanobelt solution |
| CN106128802B (en) * | 2016-07-04 | 2018-01-26 | 上海电力学院 | A kind of preparation method of electrode material for ultracapacitor |
| CN106046401B (en) * | 2016-07-07 | 2018-12-25 | 北京化工大学 | A kind of preparation method of graphene polyaniline aeroge thermoelectric material |
-
2018
- 2018-05-09 CN CN201810435311.9A patent/CN108570229B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108570229A (en) | 2018-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108570229B (en) | Graphene nanoribbon-polyaniline nanoribbon composite material and preparation method thereof | |
| Heme et al. | Recent progress in polyaniline composites for high capacity energy storage: A review | |
| Liu et al. | Recent advancements of polyaniline-based nanocomposites for supercapacitors | |
| Gao | Graphene and polymer composites for supercapacitor applications: a review | |
| Chen et al. | The development of pseudocapacitor electrodes and devices with high active mass loading | |
| Guo et al. | Research progress of nanocellulose for electrochemical energy storage: A review | |
| Luo et al. | Overview of MXene/conducting polymer composites for supercapacitors | |
| Xiang et al. | A review on electronically conducting polymers for lithium-sulfur battery and lithium-selenium battery: Progress and prospects | |
| Shi et al. | Energy gels: A bio-inspired material platform for advanced energy applications | |
| Shi et al. | Nanostructured conductive polymers for advanced energy storage | |
| Li et al. | Directly drawing self-assembled, porous, and monolithic graphene fiber from chemical vapor deposition grown graphene film and its electrochemical properties | |
| Yan et al. | Progress in the preparation and application of three-dimensional graphene-based porous nanocomposites | |
| KR101648229B1 (en) | Mesoporous metal oxide graphene nanocomposite materials | |
| Hu et al. | Silicon-conductive nanopaper for Li-ion batteries | |
| Vilatela et al. | Tough electrodes: carbon nanotube fibers as the ultimate current collectors/active material for energy management devices | |
| Zhang et al. | Electropolymerization of graphene oxide/polyaniline composite for high-performance supercapacitor | |
| CN106463276B (en) | Metal oxide anchored graphene and carbon nanotube hybrid foam | |
| Bilal et al. | Insight into capacitive performance of polyaniline/graphene oxide composites with ecofriendly binder | |
| CN107919233A (en) | A kind of high voltage flexible solid-state supercapacitor and preparation method thereof | |
| Luo et al. | Graphene oxide based conductive glue as a binder for ultracapacitor electrodes | |
| Cui et al. | Polymer/graphene hybrids for advanced energy‐conversion and‐storage materials | |
| Yasami et al. | Developed composites materials for flexible supercapacitors electrode:“Recent progress & future aspects” | |
| Yin et al. | CoNi-layered double hydroxide array on graphene-based fiber as a new electrode material for microsupercapacitor | |
| Li et al. | Ordered multiphase polymer nanocomposites for high-performance solid-state supercapacitors | |
| Göktuna et al. | Preparation and characterization of PANI: α borophene electrode for supercapacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |