CN108570229B - A kind of graphene nanobelt-polyaniline nanobelt composite material and preparation method thereof - Google Patents

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

A kind of graphene nanobelt-polyaniline nanobelt composite material and preparation method thereof

technical field

The invention belongs to the field of nanocomposite material preparation, and relates to a graphene nanobelt-polyaniline nanobelt compound material and a preparation method thereof.

Background technique

Graphene-based nanocomposites combine the excellent electron/ion transport properties, mechanical properties, and electrochemical properties of active nanomaterials, and have broad application value and market prospects in lithium batteries, supercapacitors, and other fields. In the past ten years, the research of graphene-based nanocomposites in energy storage materials, devices and technologies has made remarkable progress. However, with the development of science and technology and the improvement of material and cultural needs, people have put forward higher requirements for energy storage materials, such as high reserves, thinness, flexibility and wearability.

At present, graphene-based nanocomposites are mainly prepared by the following two methods: 1) The graphene oxide solution is blended with another nanomaterial, and then the composite material is formed by co-hydrothermal, co-deposition or in-situ polymerization. Graphene-based nanocomposites are obtained after reduction by means of reagents or atmosphere reduction, and the formed composite structure is generally a "filling" formula as shown in Figure 1, that is, nanoparticles, nanospheres or nanorods are grown in situ and then filled with graphite. The surface of the graphene sheet or between the graphene sheets; 2) The network structure is first formed by graphene oxide hydrothermal, template impregnation, etc., and then another nanomaterial is wrapped in graphite by electrochemical deposition, hydrothermal and other methods. On the surface of the alkene skeleton network, the composite structure formed after the final reduction is called the "coated" formula as shown in Figure 2.

The above two methods are simple and general, but there are still problems in summary. First, in method 1), the graphene sheets are very easy to stack, and the nanomaterials are very easy to agglomerate, which leads to the waste of nanomaterials and the decline of the performance of nanomaterials. Although method 2) can effectively avoid the stacking of graphene sheets when forming the composite material, due to the very large pore structure, the energy storage density per unit volume of the material is low. In addition, the fatal problem of both methods is that no matter whether the nanomaterials are filled in the pores or coated on the surface of the network, they are basically in the form of nanoparticles. When the material is subjected to external bending deformation, especially when it is repeatedly bent , the nanoparticles in the "filled" structure are prone to agglomeration and displacement, while the nanoparticles in the "encapsulated" structure are easily exfoliated from the network surface, resulting in a decrease in the overall material properties.

Therefore, it is of great practical significance to develop a graphene-based nanocomposite that can effectively avoid the obvious degradation of material properties caused by bending deformation.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to overcome the defects of poor bending deformation resistance and easy performance degradation of composite materials in the prior art, and to provide a graphene-based nanomaterial that can effectively avoid the obvious decline in material performance caused by bending deformation. Composite materials and methods of making the same.

To achieve the above object, the present invention adopts the following technical solutions:

A graphene nanoribbon-polyaniline nanoribbon composite material, wherein the graphene nanoribbon-polyaniline nanoribbon composite material is a composite aerogel with a network interpenetrating structure formed by graphene nanoribbons and polyaniline nanoribbons; After the graphene nanobelt-polyaniline nanobelt composite material is bent 1000 times, the specific capacitance retention rate is more than 96%. The graphene-polyaniline nanoparticle composite material in the prior art has a significant decrease in the performance of the overall composite material due to the agglomeration of nanoparticles and the loss of connection between graphene and polyaniline after being bent 400 times. After the specific capacitance of the nanocomposite decreased to about 60% of the initial value, the graphene nanoribbon-polyaniline nanoribbon composite material had a specific capacitance of 600-700F/g under the condition of a current density of 0.25A/g, while The specific capacitance of the existing "filled" and "wrapped" graphene-polyaniline nanoparticle composite materials is only 300-450 F/g. The prior art cannot take into account the large specific capacitance and the good bending resistance at the same time.

A graphene nanoribbon-polyaniline nanoribbon composite material as described above, the electrical conductivity of the graphene nanoribbon-polyaniline nanoribbon composite material is 100-1000 S/m, and due to its porous structure, the electrolyte solution is ionically fast Effectively transport; due to the three-dimensional penetration of graphene nanoribbons, it shows excellent electrical conductivity; two types of two-dimensional nanomaterials are entangled to produce synergistic effects such as double network interpenetrating structures, resulting in more excellent mechanical properties, recoverable The compressive strain is 10 to 30%.

A graphene nanoribbon-polyaniline nanoribbon composite material as described above, wherein the graphene nanoribbon has a width of 200 nm to 1 μm, a length of 3 to 20 μm, and a thickness of 5 to 50 nm; The width is 50 to 1000 nm, the length is 10 to 20 μm, and the thickness is 10 to 100 nm.

The present invention also provides a graphene nanoribbon-polyaniline nanoribbon composite material method as described above, wherein the graphene oxide nanoribbon hydrogel is successively soaked in mixed solution I and mixed solution II to obtain graphite oxide A graphene nanobelt-polyaniline nanobelt composite material, and then the graphene nanobelt-polyaniline nanobelt composite material is obtained by reduction;

The mixed solution I is mainly composed of camphorsulfonic acid, water and aniline, and the mixed solution II is mainly composed of ammonium persulfate, water, camphorsulfonic acid or phytic acid.

As the preferred technical solution:

As described above, the steps are as follows:

(1) After uniformly dispersing the carbon nanotubes in concentrated sulfuric acid, keep a certain stirring speed and add phosphoric acid and potassium permanganate in turn, and then slowly heat up to 60-80°C. Graphene oxide nanobelts are obtained; if the temperature is too low, the oxidation reaction does not proceed, and the carbon nanotubes cannot be cut; if the temperature is too high, the reaction is too violent, resulting in many defects in the nanobelts; if the temperature is too fast, the reaction rate is too large, resulting in graphite oxide The size of the ene nanoribbons is very non-uniform; the heating is too slow, resulting in too long the overall period, and the nanoribbons will be smaller in size.

(2) After the graphene oxide nanobelts are uniformly dispersed in water, a surfactant is added to obtain a stable dispersion liquid of graphene oxide nanobelts; the effect of adding a surfactant has two functions: (1) It is more conducive to the graphene oxide nanobelts (2) The surfactant is dispersed in the solution to induce the growth of polyaniline into nanobelts in the later stage, that is, the function of soft template.

(3) The stable dispersion of graphene oxide nanoribbons is hydrothermally reacted at 120-160 °C for 12-36 h to obtain graphene oxide nanoribbon hydrogel; There are also many oxygen-containing groups, which have strong negative charge and hydrophilicity, which hinder the cohesion of graphene oxide nanobelts, so that a stable three-dimensional structure cannot be formed; when the temperature increases from 120 °C to 160 °C When the oxygen-containing functional groups are gradually removed, the reduction degree of the graphene oxide nanoribbons increases, the electrostatic and hydrophilic forces weaken, and the ribbons begin to interweave and self-assemble together to form a relatively stable three-dimensional structure; With the further increase of the thermal temperature, the reduction degree of the graphene oxide nanoribbons also increases correspondingly, the cohesion force increases, the ribbons are stacked tightly, the agglomeration becomes serious, and the mesh pore size becomes smaller. When the hydrothermal reaction time is short, under the action of pressure and temperature, the electrostatic and hydrogen bonds between the bands are not fully formed, and a stable network structure cannot be obtained.

(4) After dissolving camphorsulfonic acid in water, adding aniline to prepare a uniform mixed solution I, and then immersing the graphene oxide nanobelt hydrogel in the mixed solution I at room temperature, that is, 15-25 °C for 8-24 hours; room temperature conditions The permeation rate of lower aniline is moderate. If the temperature is too high, the gel network structure will be damaged. If the temperature is too low, the permeability of aniline will be too low. Soak aniline for 8-24 hours to fully penetrate into the graphene oxide nanobelt water under the action of surfactant. In the porous structure space in the gel, if the soaking time is too short, the above effect cannot be achieved, and the soaking time is too long, which wastes time and cost.

(5) after dissolving camphorsulfonic acid or phytic acid in water, add ammonium persulfate to prepare a uniform mixed solution II, and soak the graphene oxide nanobelt hydrogel obtained in step (4) in the mixed solution II at 0 ~ After 6-48 hours of polymerization at 4°C, the graphene oxide nanoribbon-polyaniline nanoribbon composite material is obtained by washing and drying; low temperature (0-4°C) polymerization is conducive to the formation of polyaniline nanoribbons, and excessively high temperature leads to overreaction This leads to the formation of polyaniline nanorods or nanoparticles. If the polymerization time is too short, the polyaniline nanobelt will not be fully polymerized, and if the polymerization time is too long, the formed molecular chain will be oxidatively degraded in an oxidative environment, thereby reducing its electrical conductivity. The camphorsulfonic acid here provides an acidic environment, which makes aniline have good solubility and improves its electrical conductivity at the same time; ammonium persulfate is an oxidant, which enables aniline to undergo oxidative polymerization at low temperature.

(6) The graphene oxide nanoribbon-polyaniline nanoribbon composite material is dipped in a reducing agent and reacted at 80-100° C. for 4-12 hours, and the graphene nanoribbon-polyaniline nanoribbon composite material is obtained after washing and drying. This reduction treatment method can be achieved at a lower temperature below 100 °C. While removing the oxygen-containing functional groups of the graphene oxide nanobelts, the reaction products are precipitated in the form of liquid phase, and the generated capillary force improves the graphene nanobelt. Therefore, the graphene nanoribbons obtained after reduction have significant improvements in electrical conductivity, mechanical strength, and flexibility.

In the above method, in step (1), the mass ratio of the carbon nanotubes, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 15～25:6～10:1:75～125; The mass concentration is 95 to 98%; the mass concentration of the phosphoric acid is 85%; the certain stirring speed is 200 to 500 rpm; Perform cooling, standing, washing, and centrifugation. When graphene oxide nanoribbons are prepared under the condition of this oxidant/carbon nanotube mass ratio, with the increase of reaction time, the oxidation degree of graphene oxide nanoribbons will increase until it reaches saturation. Under the condition of low oxidant/carbon nanotube mass ratio, the oxidant is gradually consumed with the increase of reaction time, but when the oxidant is completely consumed or the concentration is very low, under strong acid conditions, the surface of the generated graphene oxide nanoribbons The oxygen-containing groups are gradually reduced again.

In the above-mentioned method, the cooling and standing means that after cooling to room temperature, pouring into ice water containing hydrogen peroxide and standing for 12-24 hours, the hydrogen peroxide can also remove excess potassium permanganate in addition to the cooling effect; The washing is to use dilute hydrochloric acid to wash the precipitate obtained by cooling and standing for multiple times; the centrifugation refers to centrifuging the washed precipitate 2 to 4 times with a centrifuge, and the rotation speed of the centrifuge is 8000 to 10000 rpm.

In the above method, in step (2), the surfactant is sodium dodecyl benzene sulfonate, sodium secondary alkyl sulfonate or fatty acid methyl ester ethoxylate, and the graphene oxide nanobelt is stable The concentration of the surfactant in the dispersion is 30-80 mg/mL; the concentration of the graphene oxide nanobelts in the stable dispersion of graphene oxide nanobelts is 4-10 mg/mL; in step (4), the camphorsulfonic acid The mass ratio of acid to 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 conducive to the formation of polyaniline with regular structure and higher electrical conductivity; when the acid concentration is low, the polyaniline is formed, accompanied by phenazine substances and aniline oligomers. The formation of , the product presents an aggregated structure, and its electrical conductivity is also low.

The above method, in step (5), the mass ratio of the camphorsulfonic acid or phytic acid and ammonium persulfate is 4～8:1; the concentration of ammonium persulfate in the mixed solution II is 8～50mg/ The immersion means that the graphene oxide nanobelt hydrogel is completely immersed in the mixed solution II; in step (6), the reducing agent is hydroiodic acid, vitamin C, lysine or vitamin C and lysine The mixed solution of acid, the mass ratio of the reducing agent to the graphene oxide nanobelt is 3:1. In the polymerization process, the amount of the oxidant and the concentration of the acid are conducive to the formation of polyaniline with regular structure and higher conductivity; when the amount of the oxidant is high and the acid concentration is low, the polyaniline is formed, accompanied by phenazine substances and The formation of aniline oligomers presents aggregated structures with low electrical conductivity.

In the above method, the washing in steps (5) and (6) is to alternately wash with deionized water and ethanol for 5 to 6 times, until the washing solution becomes colorless; in steps (5) and (6) The drying is freeze drying or supercritical drying.

In the above method, the drying temperature of the freeze-drying is -30～-40℃, and the drying time is 12h～48h; the drying temperature of the supercritical drying is 30～40℃, the drying pressure is 8～10MPa, and the drying time is 12h～48h. For 4h ~ 10h.

Invention Mechanism:

Due to the limitation of the existing graphene-based nanocomposite material structure, the present invention overcomes this problem by preparing nanoribbons to change the material structure.

Compared with nanostructures such as nanoparticles and nanosheets, nanoribbons have the following advantages: 1) The width is large, which increases the contact area of a single point between materials and the probability of contact between materials, which is more conducive to the establishment of electron and ion transport networks. 2) The thickness is thin, ions can enter the active material from the thickness direction, ensuring a similar diffusion distance to the linear nanomaterial; and due to the edge effect, there are more reactive sites; 3) It has excellent flexibility and can form a good flexibility When the network structure is subjected to bending deformation, it is easy to maintain the flexibility and bendability of the overall material through the adjustment of its own shape.

Polyaniline is a typical class of conductive polymers. This type of polymer has a conjugated system on the main chain, which can conduct electricity through doping. It has low cost, high doped state conductivity, high storage capacity and porosity, and voltage window. It has many advantages, such as wide width, good reversibility and tunable electrochemical activity. In addition, polyaniline also has a wide tunable capacitance range, which can be used to prepare high-conductivity, high-performance supercapacitor electrode materials. However, conductive polymers are restricted from being fully used in supercapacitors due to their poor conductivity and slow electron transfer speed. Therefore, it is of great significance to composite polyaniline with other highly conductive carbon materials.

The present invention constructs a network interpenetrating structure of graphene nanoribbons and polyaniline nanoribbons as shown in FIG. 3 , and the nanocomposite material will have the following advantages: 1) It has three-dimensional connected pores, which is conducive to the rapid and comprehensive operation of electrolyte ions. 2) The nanobelt has a very small thickness, which reduces the ion diffusion distance, thereby improving the material utilization rate; 3) The nanomaterial and the graphene nanoribbon penetrate/entangle with each other, forming a 4) Under the action of external bending stress, the interpenetrating network formed by nanoribbons has better bending resistance due to its flexibility and mutual slippage.

Beneficial effects:

(1) The preparation method of a graphene nanoribbon-polyaniline nanoribbon composite material of the present invention has the advantages of simple preparation process, easy operation, ingenious design, and great promotion value;

(2) A graphene nanoribbon-polyaniline nanoribbon composite material of the present invention is based on graphene nanoribbons, and the unique aspect ratio and edge structure of graphene nanoribbons endow it with a high specific surface area, while graphite The alkene nanoribbons have excellent electrical conductivity, and their lamellar structure enables electrons and ions to be transported quickly and efficiently in the electrocatalytic process; the composite of quasi-one-dimensional materials and two-dimensional materials is realized by a hydrothermal method, so that the advantages of both can be realized. Give full play to the construction of composite materials with excellent properties;

(3) A graphene nanoribbon-polyaniline nanoribbon composite material of the present invention can be used as a high-performance supercapacitor electrode material and an ideal electrode material for new energy sources such as lithium ion batteries and solar cells, and has great application prospects.

Description of drawings

Fig. 1 is the structural representation of "filled type" composite structure graphene-based nanocomposite;

Fig. 2 is the structural representation of "wrapped" composite structure graphene-based nanocomposite;

3 is a schematic structural diagram of a graphene nanoribbon-polyaniline nanoribbon composite material of the present invention;

Fig. 4 is the schematic diagram of bending test on graphene/polyaniline nanocomposite;

Fig. 5 is a comparative diagram of the effect of bending on the specific capacitance of graphene/polyaniline nanocomposite materials (A is the graphene nanoribbon-polyaniline nanoribbon composite material of the present invention, and B is graphene/polyaniline nanoparticle);

Among them, 1-graphene, 2-filled nanomaterials, 3-outsourcing nanomaterials, 4-graphene skeleton, 5-polyaniline nanobelts, 6-graphene nanobelts.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

A preparation method of graphene nanobelt-polyaniline nanobelt composite material, the preparation steps are as follows:

(1) After uniformly dispersing the carbon nanotubes in the concentrated sulfuric acid, add phosphoric acid and potassium permanganate in turn at a stirring speed of 300 rpm, and then slowly heat up to 70 °C at a heating rate of 5 °C/min. After the temperature is stable, keep warm After cooling to room temperature for 2 hours, pour it into ice water containing hydrogen peroxide and let stand for 12 hours, then use dilute hydrochloric acid to wash the precipitate obtained by cooling and standing for several times, and finally centrifuge the washed precipitate for 2 times. Graphene oxide nanobelts are obtained, wherein the mass ratio of carbon nanotubes, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 15:6:1:75, the mass concentration of concentrated sulfuric acid is 98%, and the mass concentration of phosphoric acid is 85%, The speed of the centrifuge is 9000rpm;

(2) adding sodium dodecyl benzene sulfonate after uniformly dispersing the graphene oxide nanoribbons in water to obtain a stable dispersion liquid of graphene oxide nanoribbons, wherein the graphene oxide nanoribbons in the stable dispersion liquid of graphene oxide nanoribbons The concentration of sodium dodecylbenzene sulfonate is 4mg/mL, and the concentration of sodium dodecylbenzenesulfonate is 50mg/mL;

(3) The stable dispersion of graphene oxide nanoribbons is hydrothermally reacted at 120 °C for 14 h to obtain a graphene oxide nanoribbon hydrogel;

(4) After dissolving camphorsulfonic acid in water, add aniline to prepare a uniform mixed solution I, and then immerse the graphene oxide nanobelt hydrogel in the mixed solution I at 20°C for 16 h, wherein the mass ratio of camphorsulfonic acid to aniline It is 3:1, and the concentration of aniline in the mixed solution I is 15mg/mL;

(5) After the camphorsulfonic acid is dissolved in water, ammonium persulfate is added to prepare a uniform mixed solution II, and the graphene oxide nanoribbon hydrogel obtained by the treatment in step (4) is completely immersed in the mixed solution II and polymerized at 2° C. After 24 hours, alternately washed 6 times with deionized water and ethanol, until the washing solution became colorless, and obtained the graphene oxide nanobelt-polyaniline nanobelt composite material after freeze-drying, wherein camphorsulfonic acid and ammonium persulfate The mass ratio of ammonium persulfate is 5:1, the concentration of ammonium persulfate in mixed solution II is 20mg/mL, the drying temperature of freeze-drying is -35°C, and the drying time is 40h;

(6) First, the graphene oxide nanoribbon-polyaniline nanocomposite was immersed in hydroiodic acid and reacted at 90 °C for 8 h, and then washed with deionized water and ethanol alternately for 6 times until the washing solution became colorless, The graphene nanoribbon-polyaniline nanoribbon composite material is obtained after freeze-drying, wherein the mass ratio of hydroiodic acid and graphene oxide nanoribbon is 3:1, the drying temperature of freeze-drying is -35°C, and the drying time is 30h.

The graphene nanoribbon-polyaniline nanoribbon composite material finally prepared is a composite aerogel with a network interpenetrating structure formed by graphene nanoribbons and polyaniline nanoribbons. The width of the graphene nanoribbons is 600 nm and the length is 12 μm. , the thickness is 45 nm, the width of the polyaniline nanoribbon is 500 nm, the length is 15 μm, and the thickness is 50 nm. 28%, and the specific capacitance is 700F/g at a current density of 0.25A/g.

The specific capacitance (F/g) of the material was obtained by cyclic voltammetry in an electrochemical workstation, and after bending it several times according to the method shown in Figure 4 (fix the sample on the substrate with a clamp, and bend it by 150° according to the dotted line), The specific capacitance of the material was re-tested to characterize the effect of bending on the specific capacitance properties of the graphene nanoribbon/polyaniline nanoribbon composite, and the specific capacitance retention rate of the graphene nanoribbon-polyaniline nanoribbon composite was measured to be 96% .

Comparative Example 1

A method for preparing a graphene-polyaniline nanoparticle composite material. A "filled" graphene-polyaniline nanoparticle composite material is prepared by in-situ polymerization of a graphene oxide solution and aniline. The obtained graphene-polyaniline nanoparticle composite material is subjected to the same bending test as in Example 1, the graphene nanoribbon-polyaniline nanoribbon composite material obtained in Example 1 and the graphene obtained in Comparative Example 1 The specific capacitance change curve when the polyaniline nanoparticle composite material is subjected to a bending test is shown in Figure 5. In the figure, A is the graphene nanoribbon-polyaniline nanoribbon composite material of the present invention, and B is the graphene-polyaniline nanoparticle The composite material, as can be seen from Figure 5, after 1000 times of bending, the specific capacitance retention rate of the graphene nanoribbon-polyaniline nanoribbon composite material of the present invention is still about 96%; After 400 times of bending, the performance of the overall composite material decreased significantly due to the agglomeration of polyaniline nanoparticles and the two-phase separation of polyaniline and graphene. %, and the specific capacitance is 330F/g under the condition of a current density of 0.25A/g. The graphene nanoribbon-polyaniline nanoribbon composite material prepared by the invention has excellent bending deformation resistance, which has achieved remarkable progress compared with the prior art.

Comparative Example 2

A preparation method of carbon nanotube-polyaniline nanobelt composite material, the preparation steps are as follows:

(1) Add sodium dodecyl benzene sulfonate to water at a concentration of 50 mg/mL, then add single-walled carbon nanotubes, and ultrasonically disperse for 4 hours to obtain a stable dispersion of carbon nanotubes, in which the single-walled carbon nanotubes are dispersed. The concentration of 8mg/mL;

(2) ultrasonically dispersing the single-walled carbon nanotube solution for 16 hours to obtain a single-walled carbon nanotube gel;

(3) After dissolving camphorsulfonic acid in water, add aniline to prepare a uniform mixed solution I, and then immerse the carbon nanotube hydrogel in the mixed solution I at 20°C for 16 hours, wherein the mass ratio of camphorsulfonic acid to aniline is 3 : 1, the concentration of aniline in mixed solution 1 is 15mg/mL;

(4) After dissolving camphorsulfonic acid in water, adding ammonium persulfate to prepare a uniform mixed solution II, immersing the carbon nanotube hydrogel obtained in step (3) in the mixed solution II and polymerizing at 2°C for 24 hours , alternately wash 6 times with deionized water and ethanol, until the washing solution becomes colorless, after freeze-drying, the carbon nanotube-polyaniline nanobelt composite material is obtained, wherein the mass ratio of camphorsulfonic acid and ammonium persulfate is 5:1, the concentration of ammonium persulfate in mixed solution II is 20 mg/mL, the drying temperature of freeze-drying is -35°C, and the drying time is 40h.

In the finally prepared carbon nanotube-polyaniline nanobelt composite material, the polyaniline nanobelt and carbon nanotube form a network interpenetrating structure, and the specific capacitance is 450F/g under the condition of a current density of 0.25A/g. After 1000 times of bending, the specific capacitance retention rate is 94%. Compared with Example 1, it can be found that the bending resistance of the two is similar, and the excellent bending resistance is derived from the network interpenetrating structure. However, in the present invention, the specific capacitance of the graphene nanoribbon-polyaniline nanoribbon can reach 700 F/g, which is far better than that of the carbon nanotube-polyaniline nanoribbon composite material. The larger the size of the ribbon, the larger the space in the network structure formed by it, which is more favorable for the growth of PANI nanobelts, so the PANI content in the composite material is higher, resulting in a higher specific capacitance of the final composite material.

Example 2

A preparation method of graphene nanobelt-polyaniline nanobelt composite material, the preparation steps are as follows:

(1) After uniformly dispersing the carbon nanotubes in concentrated sulfuric acid, add phosphoric acid and potassium permanganate in turn at a stirring speed of 200 rpm, and then slowly heat up to 60 °C at a heating rate of 5 °C/min. After the temperature is stable, keep the temperature After cooling to room temperature for 2 hours, pour it into ice water containing hydrogen peroxide and let stand for 12 hours, then use dilute hydrochloric acid to wash the precipitate obtained by cooling and standing for several times, and finally centrifuge the washed precipitate for 2 times. Obtain graphene oxide nanobelt, wherein the mass ratio of carbon nanotubes, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 15:6:1:75, the mass concentration of concentrated sulfuric acid is 95%, and the mass concentration of phosphoric acid is 85%, The speed of the centrifuge is 8000rpm;

(2) after the graphene oxide nanobelts are uniformly dispersed in water, sodium secondary alkyl sulfonate is added to obtain a stable dispersion liquid of graphene oxide nanobelts, wherein the concentration of graphene oxide nanobelts in the stable dispersion liquid of graphene oxide nanobelts is 4 mg/mL, and the concentration of sodium secondary alkyl sulfonate is 30 mg/mL;

(3) The stable dispersion of graphene oxide nanoribbons is hydrothermally reacted at 120 °C for 12 h to obtain a graphene oxide nanoribbon hydrogel;

(4) After dissolving camphorsulfonic acid in water, add aniline to prepare a uniform mixed solution I, and then immerse the graphene oxide nanobelt hydrogel in the mixed solution I at 15°C for 8 h, wherein the mass ratio of camphorsulfonic acid to aniline It is 2:1, and the concentration of aniline in the mixed solution I is 5mg/mL;

(5) After phytic acid is dissolved in water, ammonium persulfate is added to prepare a uniform mixed solution II, and the graphene oxide nanoribbon hydrogel obtained in step (4) is completely immersed in the mixed solution II and polymerized at 0 °C for 6 h Then, alternately wash 6 times with deionized water and ethanol, until the washing solution becomes colorless, after freeze-drying, the graphene oxide nanobelt-polyaniline nanobelt composite material is obtained, wherein the quality of phytic acid and ammonium persulfate is The ratio is 4:1, the concentration of ammonium persulfate in mixed solution II is 8 mg/mL, the drying temperature of freeze-drying is -30°C, and the drying time is 48h;

(6) First, the graphene oxide nanoribbon-polyaniline nanoribbon composite material was immersed in vitamin C and reacted at 80 °C for 8 h, and then washed with deionized water and ethanol alternately for 6 times until the washing solution became colorless, The graphene nanoribbon-polyaniline nanoribbon composite material is obtained after freeze-drying, wherein the mass ratio of vitamin C to the graphene oxide nanoribbon is 3:1, the drying temperature of freeze-drying is -30°C, and the drying time is 48h.

The graphene nanoribbon-polyaniline nanoribbon composite material finally prepared is a composite aerogel with a network interpenetrating structure formed by graphene nanoribbons and polyaniline nanoribbons. The width of the graphene nanoribbons is 200 nm and the length is 20 μm. , the thickness is 50 nm, the width of the polyaniline nanoribbon is 1000 nm, the length is 20 μm, and the thickness is 100 nm. 10%, its specific capacitance is 600F/g under the condition of current density of 0.25A/g, and the specific capacitance retention rate of graphene nanoribbon-polyaniline nanoribbon composite is 96.2% after bending 1000 times.

Example 3

A preparation method of graphene nanobelt-polyaniline nanobelt composite material, the preparation steps are as follows:

(1) After uniformly dispersing the carbon nanotubes in concentrated sulfuric acid, add phosphoric acid and potassium permanganate in turn at a stirring speed of 500 rpm, and then slowly heat up to 80 °C at a heating rate of 10 °C/min. After the temperature is stable, keep warm After cooling to room temperature for 3 hours, pour it into ice water containing hydrogen peroxide and let it stand for 24 hours, then use dilute hydrochloric acid to wash the precipitate obtained by cooling and standing for several times, and finally centrifuge the washed precipitate for 4 times. Graphene oxide nanobelts are obtained, wherein the mass ratio of carbon nanotubes, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 25:10:1:125, the mass concentration of concentrated sulfuric acid is 98%, and the mass concentration of phosphoric acid is 85%, The speed of the centrifuge is 10000rpm;

(2) after the graphene oxide nanobelt is uniformly dispersed in water, sodium methyl stearate polyoxyethylene ether sulfonate is added to obtain a graphene oxide nanobelt stable dispersion, wherein the graphene oxide nanobelt stabilized dispersion is oxidized The concentration of graphene nanoribbon is 10mg/mL, and the concentration of methyl stearate polyoxyethylene ether sulfonate sodium is 80mg/mL;

(3) The stable dispersion of graphene oxide nanoribbons is hydrothermally reacted at 160 °C for 36 h to obtain a graphene oxide nanoribbon hydrogel;

(4) After dissolving camphorsulfonic acid in water, add aniline to prepare a uniform mixed solution I, and then immerse the graphene oxide nanobelt hydrogel in the mixed solution I at 25°C for 24 hours, wherein the mass ratio of camphorsulfonic acid to aniline It is 4:1, and the concentration of aniline in mixed solution I is 25mg/mL;

(5) After the camphorsulfonic acid is dissolved in the water, ammonium persulfate is added to prepare a uniform mixed solution II, and the graphene oxide nanoribbon hydrogel obtained by the step (4) is completely immersed in the mixed solution II and polymerized at 4° C. After 48 hours, alternately wash with deionized water and ethanol for 5 times, until the washing solution becomes colorless, after freeze-drying, the graphene oxide nanobelt-polyaniline nanobelt composite material is obtained, wherein camphorsulfonic acid and ammonium persulfate The mass ratio of ammonium persulfate is 8:1, the concentration of ammonium persulfate in mixed solution II is 50 mg/mL, the drying temperature of freeze-drying is -40 °C, and the drying time is 12 h;

(6) First, the graphene oxide nanoribbon-polyaniline nanoribbon composite material was immersed in lysine and reacted at 100 °C for 12 h, and then washed with deionized water and ethanol alternately for 5 times until the washing solution became colorless. , the graphene nanoribbon-polyaniline nanoribbon composite material is obtained after freeze-drying, wherein the mass ratio of lysine and graphene oxide nanoribbon is 3:1, the drying temperature of freeze-drying is -40°C, and the drying time is 12h .

The graphene nanoribbon-polyaniline nanoribbon composite material finally prepared is a composite aerogel with a network interpenetrating structure formed by graphene nanoribbons and polyaniline nanoribbons. The width of the graphene nanoribbons is 1 μm and the length is 3 μm. , the thickness is 5 nm, the width of the polyaniline nanoribbon is 50 nm, the length is 10 μm, and the thickness is 10 nm. 15%, the specific capacitance is 650F/g under the condition of current density of 0.25A/g, and the specific capacitance retention rate of graphene nanoribbon-polyaniline nanoribbon composite is 96.5% after 1000 times of bending.

Example 4

A preparation method of graphene nanobelt-polyaniline nanobelt composite material, the preparation steps are as follows:

(1) After uniformly dispersing the carbon nanotubes in concentrated sulfuric acid, add phosphoric acid and potassium permanganate in turn at a stirring speed of 300 rpm, and then slowly heat up to 65 °C at a heating rate of 7 °C/min. After the temperature is stable, keep the temperature After cooling to room temperature for 2 hours, pour it into ice water containing hydrogen peroxide and let it stand for 16 hours, then use dilute hydrochloric acid to wash the precipitate obtained by cooling and standing for several times, and finally centrifuge the washed precipitate for 3 times. Graphene oxide nanobelts are obtained, wherein the mass ratio of carbon nanotubes, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 18:8:1:80, the mass concentration of concentrated sulfuric acid is 96%, and the mass concentration of phosphoric acid is 85%, The speed of the centrifuge is 8500rpm;

(2) adding sodium dodecyl benzene sulfonate after uniformly dispersing the graphene oxide nanoribbons in water to obtain a stable dispersion liquid of graphene oxide nanoribbons, wherein the graphene oxide nanoribbons in the stable dispersion liquid of graphene oxide nanoribbons The concentration of sodium dodecylbenzenesulfonate is 5mg/mL, and the concentration of sodium dodecylbenzenesulfonate is 40mg/mL;

(3) The stable dispersion of graphene oxide nanoribbons is hydrothermally reacted at 140 °C for 18 h to obtain a graphene oxide nanoribbon hydrogel;

(4) After dissolving camphorsulfonic acid in water, add aniline to prepare a uniform mixed solution I, and then immerse the graphene oxide nanobelt hydrogel in the mixed solution I at 20°C for 20 h, wherein the mass ratio of camphorsulfonic acid to aniline It is 2:1, and the concentration of aniline in the mixed solution I is 20mg/mL;

(5) After the camphorsulfonic acid is dissolved in water, ammonium persulfate is added to prepare a uniform mixed solution II, and the graphene oxide nanoribbon hydrogel obtained by the treatment in step (4) is completely immersed in the mixed solution II and polymerized at 0° C. After 8 hours, alternately washed with deionized water and ethanol for 6 times until the washing solution became colorless, and after freeze-drying, the graphene oxide nanobelt-polyaniline nanobelt composite material was obtained, wherein camphorsulfonic acid and ammonium persulfate The mass ratio of ammonium persulfate is 6:1, the concentration of ammonium persulfate in mixed solution II is 15mg/mL, the drying temperature of freeze-drying is -35℃, and the drying time is 20h;

(6) First, the graphene oxide nanoribbon-polyaniline nanoribbon composite material was immersed in a mixed solution of vitamin C and lysine (mass ratio 1:1) for 6 h at 90 °C, and then deionized water and ethanol were used for the reaction. Alternately washed 6 times, until the washing solution becomes colorless, after freeze-drying, the graphene nanobelt-polyaniline nanobelt composite material is obtained, wherein the mixed solution of vitamin C and lysine and the quality of the graphene oxide nanobelt are obtained. The ratio is 3:1, the drying temperature of freeze-drying is -35°C, and the drying time is 20h.

The graphene nanoribbon-polyaniline nanoribbon composite material finally prepared is a composite aerogel with a network interpenetrating structure formed by graphene nanoribbons and polyaniline nanoribbons. The width of the graphene nanoribbons is 400 nm and the length is 10 μm. , the thickness is 20 nm, the width of the polyaniline nanoribbon is 200 nm, the length is 15 μm, and the thickness is 30 nm. 20%, the specific capacitance is 680F/g under the condition of current density of 0.25A/g, and the specific capacitance retention rate of graphene nanoribbon-polyaniline nanoribbon composite is 97% after bending 1000 times.

Example 5

A preparation method of graphene nanobelt-polyaniline nanobelt composite material, the preparation steps are as follows:

(1) After uniformly dispersing the carbon nanotubes in concentrated sulfuric acid, add phosphoric acid and potassium permanganate in turn at a stirring speed of 400 rpm, and then slowly heat up to 70 °C at a heating rate of 10 °C/min. After the temperature is stable, keep the temperature After cooling to room temperature for 3 hours, pour it into ice water containing hydrogen peroxide and let it stand for 20 hours, then use dilute hydrochloric acid to wash the precipitate obtained by cooling and standing for several times, and finally centrifuge the washed precipitate for 2 times. Graphene oxide nanobelts are obtained, wherein the mass ratio of carbon nanotubes, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 20:10:1:120, the mass concentration of concentrated sulfuric acid is 97%, and the mass concentration of phosphoric acid is 85%, The speed of the centrifuge is 9000rpm;

(2) adding sodium dodecyl benzene sulfonate after uniformly dispersing the graphene oxide nanoribbons in water to obtain a stable dispersion liquid of graphene oxide nanoribbons, wherein the graphene oxide nanoribbons in the stable dispersion liquid of graphene oxide nanoribbons The concentration of sodium dodecylbenzenesulfonate is 8mg/mL, and the concentration of sodium dodecylbenzenesulfonate is 60mg/mL;

(3) The stable dispersion of graphene oxide nanoribbons is hydrothermally reacted at 150 °C for 25 h to obtain a graphene oxide nanoribbon hydrogel;

(4) After dissolving camphorsulfonic acid in water, add aniline to prepare a uniform mixed solution I, and then immerse the graphene oxide nanobelt hydrogel in the mixed solution I at 25°C for 24 hours, wherein the mass ratio of camphorsulfonic acid to aniline It is 4:1, and the concentration of aniline in mixed solution I is 20mg/mL;

(5) After the camphorsulfonic acid is dissolved in water, ammonium persulfate is added to prepare a uniform mixed solution II, and the graphene oxide nanoribbon hydrogel obtained by the treatment in step (4) is completely immersed in the mixed solution II and polymerized at 0° C. After 6h, alternately wash with deionized water and ethanol for 5 times until the washing solution becomes colorless, and after supercritical drying, the graphene oxide nanobelt-polyaniline nanobelt composite material is obtained, wherein camphorsulfonic acid and persulfuric acid are obtained. The mass ratio of ammonium is 7:1, the concentration of ammonium persulfate in mixed solution II is 30mg/mL, the drying temperature of supercritical drying is 40°C, the drying pressure is 10MPa, and the drying time is 10h;

(6) First, the graphene oxide nanoribbon-polyaniline nanoribbon composite material was immersed in hydroiodic acid for 10 h at 80 °C, and then washed alternately with deionized water and ethanol for 5 times until the washing solution became colorless. , the graphene nanoribbon-polyaniline nanoribbon composite material is obtained after supercritical drying, wherein the mass ratio of hydroiodic acid and graphene oxide nanoribbon is 3:1, the drying temperature of supercritical drying is 40 ° C, and the drying pressure is 10MPa, and the drying time is 10h.

The final graphene nanoribbon-polyaniline nanoribbon composite material is a composite aerogel with a network interpenetrating structure formed by graphene nanoribbons and polyaniline nanoribbons. The width of the graphene nanoribbons is 800 nm and the length is 10 μm. , the thickness is 40 nm, the width of the polyaniline nanoribbon is 700 nm, the length is 20 μm, and the thickness is 80 nm. 25%, the specific capacitance is 640F/g under the condition of current density of 0.25A/g, and the specific capacitance retention rate of graphene nanoribbon-polyaniline nanoribbon composite is 96.7% after 1000 times of bending.

Example 6

A preparation method of graphene nanobelt-polyaniline nanobelt composite material, the preparation steps are as follows:

(1) After uniformly dispersing the carbon nanotubes in concentrated sulfuric acid, add phosphoric acid and potassium permanganate in turn at a stirring speed of 500 rpm, and then slowly heat up to 60 °C at a heating rate of 8 °C/min. After the temperature is stable, keep warm After cooling to room temperature for 3 hours, pour it into ice water containing hydrogen peroxide and let it stand for 20 hours, then use dilute hydrochloric acid to wash the precipitate obtained by cooling and standing for several times, and finally centrifuge the washed precipitate for 4 times. Graphene oxide nanobelts are obtained, wherein the mass ratio of carbon nanotubes, concentrated sulfuric acid, phosphoric acid and potassium permanganate is 25:6:1:100, the mass concentration of concentrated sulfuric acid is 95%, and the mass concentration of phosphoric acid is 85%, The speed of the centrifuge is 9500rpm;

(2) after the graphene oxide nanobelts are uniformly dispersed in water, sodium secondary alkyl sulfonate is added to obtain a stable dispersion liquid of graphene oxide nanobelts, wherein the concentration of graphene oxide nanobelts in the stable dispersion liquid of graphene oxide nanobelts is 10mg/mL, and the concentration of sodium secondary alkyl sulfonate is 50mg/mL;

(3) The stable dispersion of graphene oxide nanoribbons is hydrothermally reacted at 160 °C for 36 h to obtain a graphene oxide nanoribbon hydrogel;

(4) After dissolving camphorsulfonic acid in water, add aniline to prepare a uniform mixed solution I, and then immerse the graphene oxide nanobelt hydrogel in the mixed solution I at 20°C for 20 h, wherein the mass ratio of camphorsulfonic acid to aniline It is 4:1, and the concentration of aniline in mixed solution I is 20mg/mL;

(5) After the camphorsulfonic acid is dissolved in the water, ammonium persulfate is added to prepare a uniform mixed solution II, and the graphene oxide nanoribbon hydrogel obtained by the treatment in step (4) is completely immersed in the mixed solution II and polymerized at 3° C. After 18 hours, alternately wash with deionized water and ethanol for 6 times, until the washing solution becomes colorless, and after supercritical drying, the graphene oxide nanobelt-polyaniline nanobelt composite material is obtained, wherein camphorsulfonic acid and persulfuric acid are obtained. The mass ratio of ammonium is 5:1, the concentration of ammonium persulfate in mixed solution II is 40mg/mL, the drying temperature of supercritical drying is 30°C, the drying pressure is 8MPa, and the drying time is 4h;

(6) First, the graphene oxide nanoribbon-polyaniline nanoribbon composite material was immersed in vitamin C and reacted at 85 °C for 10 h, and then washed with deionized water and ethanol alternately for 6 times until the washing solution became colorless, The graphene nanoribbon-polyaniline nanoribbon composite material is obtained after supercritical drying, wherein the mass ratio of vitamin C and graphene oxide nanoribbon is 3:1, the drying temperature of supercritical drying is 30 ° C, and the drying pressure is 8 MPa , the drying time is 4h.

The graphene nanoribbon-polyaniline nanoribbon composite material finally prepared is a composite aerogel with a network interpenetrating structure formed by graphene nanoribbons and polyaniline nanoribbons. The width of the graphene nanoribbons is 1 μm and the length is 20 μm. , the thickness is 40 nm, the width of the polyaniline nanoribbon is 700 nm, the length is 15 μm, and the thickness is 80 nm. 25%, the specific capacitance is 630F/g under the condition of current density of 0.25A/g, and the specific capacitance retention rate of graphene nanoribbon-polyaniline nanoribbon composite is 97.2% after bending 1000 times.

Claims (9)

1. a preparation method of graphene nanobelt-polyaniline nanobelt composite material, is characterized in that, concrete steps are as follows: (1) After evenly dispersing the carbon nanotubes in sulfuric acid with a mass concentration of 95-98%, keeping a certain stirring speed, adding phosphoric acid and potassium permanganate in turn, and then slowly heating up to 60-80 °C, and keeping the temperature after the temperature is stable. 2～3h, separate the product to obtain graphene oxide nanoribbons; (2) adding a surfactant after uniformly dispersing the graphene oxide nanoribbons in water to obtain a stable dispersion liquid of the graphene oxide nanoribbons; (3) The stable dispersion of graphene oxide nanoribbons is hydrothermally reacted at 120-160 °C for 12-36 h to obtain a graphene oxide nanoribbon hydrogel; (4) After dissolving camphorsulfonic acid in water, adding aniline to prepare a uniform mixed solution I, and then immersing the graphene oxide nanobelt hydrogel in the mixed solution I at 15 to 25° C. for 8 to 24 hours; (5) after dissolving camphorsulfonic acid or phytic acid in water, add ammonium persulfate to prepare a uniform mixed solution II, and soak the graphene oxide nanobelt hydrogel obtained in step (4) in the mixed solution II at 0 ~ After being polymerized at 4°C for 6-48 hours, the graphene oxide nanoribbon-polyaniline nanoribbon composite material is obtained by washing and drying; (6) Immerse the graphene oxide nanoribbon-polyaniline nanocomposite material in a reducing agent, react at 80-100° C. for 4-12 hours, wash and dry to obtain a graphene nanoribbon-polyaniline nanobelt composite material. 2. the preparation method of a kind of graphene nanobelt-polyaniline nanobelt composite material according to claim 1, is characterized in that, in step (1), described carbon nanotube, sulfuric acid, phosphoric acid and potassium permanganate The mass ratio of the phosphoric acid is 15～25:6～10:1:75～125; the mass concentration of the phosphoric acid is 85%; the certain stirring speed is 200～500rpm; the heating rate of the slow temperature rise is 5～10 °C/min; the separated product is subjected to cooling and standing, washing and centrifugation in sequence. 3. the preparation method of a kind of graphene nanobelt-polyaniline nanobelt composite material according to claim 2, is characterized in that, described cooling standstill refers to after being cooled to room temperature, pours the ice containing hydrogen peroxide Let stand in water for 12 to 24 hours; the cleaning is to use hydrochloric acid to wash the precipitate obtained by cooling and stand for multiple times; the centrifugation refers to centrifuging the washed precipitate 2 to 4 times with a centrifuge, and the speed of the centrifuge is 8000 ~10000rpm. 4. the preparation method of a kind of graphene nanobelt-polyaniline nanobelt composite material according to claim 1, is characterized in that, in step (2), described surfactant is sodium dodecylbenzene sulfonate , sodium secondary alkyl sulfonate or fatty acid methyl ester ethoxy compound, the concentration of surfactant in the graphene oxide nanobelt stable dispersion is 30-80 mg/mL; in the graphene oxide nanobelt stable dispersion The concentration of the graphene oxide nanobelt is 4～10mg/mL; in step (4), the mass ratio of the camphorsulfonic acid to aniline is 2～4:1; the concentration of aniline in the mixed solution I is 5～25mg /mL; in step (5), the mass ratio of the camphorsulfonic acid or phytic acid to ammonium persulfate is 4 to 8:1; the concentration of ammonium persulfate in the mixed solution II is 8 to 50 mg/mL; The immersion means that the graphene oxide nanobelt hydrogel is completely immersed in the mixed solution II; in step (6), the reducing agent is hydroiodic acid, vitamin C, lysine or a mixture of vitamin C and lysine solution, the mass ratio of the reducing agent to the graphene oxide nanobelt is 3:1. 5. the preparation method of a kind of graphene nanobelt-polyaniline nanobelt composite material according to claim 1, is characterized in that, washing in step (5) and step (6) is to alternate with deionized water and ethanol Wash for 5-6 times until the washing solution becomes colorless; the drying in step (5) and step (6) is freeze drying or supercritical drying. 6. the preparation method of a kind of graphene nanoribbon-polyaniline nanoribbon composite material according to claim 5, is characterized in that, the drying temperature of described freeze-drying is -30～-40 ℃, and drying time is 12h～48h ; The drying temperature of the supercritical drying is 30-40 DEG C, the drying pressure is 8-10MPa, and the drying time is 4h-10h. 7. a kind of graphene nanobelt-polyaniline nanobelt composite material obtained by the preparation method of a kind of graphene nanobelt-polyaniline nanobelt composite material according to any one of claims 1 to 6, it is characterized in that It is: the graphene nanoribbon-polyaniline nanoribbon composite material is a composite aerogel with a network interpenetrating structure formed by graphene nanoribbons and polyaniline nanoribbons; the graphene nanoribbon-polyaniline nanoribbon composite material After the material is bent for 1000 times, the specific capacitance retention rate is more than 96%, and the specific capacitance of the graphene nanoribbon-polyaniline nanoribbon composite material is 600-700F/g under the condition of a current density of 0.25A/g . 8. A graphene nanoribbon-polyaniline nanoribbon composite material according to claim 7, wherein the electrical conductivity of the graphene nanoribbon-polyaniline nanoribbon composite material is 100-1000 S/m, The recoverable compressive strain is 10-30%. 9 . The graphene nanoribbon-polyaniline nanoribbon composite material according to claim 7 , wherein the graphene nanoribbon has a width of 200 nm to 1 μm, a length of 3 to 20 μm, and a thickness of 5 to 1 μm. 10 . 50 nm; the width of the polyaniline nanobelt is 50-1000 nm, the length is 10-20 μm, and the thickness is 10-100 nm.

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