CN107180706A - The preparation method and application of dyefunctionalized grapheme/polyaniline composite material - Google Patents

Abstract

The invention provides a preparation method and application of a dye-functionalized graphene/polyaniline composite material, belonging to the technical field of composite material preparation. The preparation method of the dye-functionalized graphene/polyaniline composite material of the present invention is to first prepare graphene oxide with a large specific surface area, then take a certain amount of dye and mix evenly with graphene oxide, and add aniline monomer under acidic conditions; After stirring evenly, keep it warm at the selected temperature, then add the acidic solution of the initiator, and react at the selected temperature for a certain period of time to obtain the dye-functionalized graphene oxide/polyaniline composite material, and then the composite is made under the action of the reducing agent The dye-functionalized graphene/polyaniline composite material can be obtained through reduction, and the prepared dye-functionalized graphene/polyaniline composite material can be used as a supercapacitor electrode material. The preparation method of the invention is simple and easy, and the specific capacitance of the composite material is large. This method provides a new method for the application of composite materials in supercapacitors.

Description

Preparation method and application of dye functionalized graphene/polyaniline composite material

technical field

The invention belongs to the technical field of preparation of composite materials, and more specifically relates to a preparation method and application of a dye-functionalized graphene/polyaniline composite material.

Background technique

As one of the conductive polymers with large theoretical specific capacitance, polyaniline has always attracted people's attention. However, as the electrode material of supercapacitor, polyaniline is prone to volume expansion during the actual charge and discharge process, which leads to its cycle stability. Poor, which also limits the application of polyaniline in supercapacitors. Therefore, it is critical to find a framework material with better stability for polyaniline, so that it can grow uniformly on the framework material and improve its stability. At present, the framework materials used to grow polyaniline are carbon nanotubes ( Wu T M, Lin Y W, Liao C S. Preparation and characterization of polyaniline/multi-walled carbon nanotube composites. Carbon, 2005, 43: 734-740.), carbon nanohorn (Maiti S, Khatua B B. Polyaniline integrated carbon nanohorn: A superior electrode materials for advanced energy storage. Express Polymer Letters, 2014, 8:895-907.), carbon cloth (Zhong M, SongY, Li Y, et al. Effect of reduced graphene oxide on the properties of anactivated carbon cloth/polyaniline flexible electrode for supercapacitor application. Journal of Power Sources, 2012, 217: 6-12.), graphene (Wu Q, Xu Y, Yao Z, et al. Supercapacitors based on flexible graphene/polyanilinenanofiber composite films. ACS nano, 2010, 4 : 1963-1970.), etc. Among them, in addition to the advantages of the above-mentioned carbon materials, graphene also has the advantages of ultra-high thermal conductivity, excellent mechanical properties, and ultra-high specific surface area. However, in practical applications, graphene is very easy to agglomerate, which greatly reduces the role of the graphene skeleton, and because there are no functional groups on the surface of graphene, its dispersibility and solubility are poor, making polyaniline unable to grow uniformly on graphene sheets, thus limiting the overall performance of the composite. Therefore, it is particularly important to modify graphene to avoid its agglomeration and allow it to give full play to the stability of the skeleton.

Graphene functionalization is mainly divided into covalent functionalized graphene and non-covalent functionalized graphene. Covalent functionalization can improve the performance of graphene, including opening its energy gap, tuning its conductivity, and improving its solubility and stability. sex etc. The non-covalent functionalization of graphene mainly utilizes the p-p* conjugation between aromatic molecules and the graphene substrate, such as porphyrin or perylene. Since the covalently functionalized graphene is easy to destroy the p-conjugated conductivity of graphene, the excellent performance of graphene is reduced (Uddin M E, Layek R K, Kim H Y, et al. Preparation and enhanced mechanical properties of non-covalently-functionalized graphene oxide/ cellulose acetatenanocomposites. Composites Part B Engineering, 2016, 90:223-231), the non-covalent functionalization of graphene is beneficial to maintain the electronic structure of graphene. However, due to the relative inertness of graphene and its limited dispersion in solvents, its functionalization still has problems of complex process and efficiency.

The present invention utilizes conjugated dye molecules to functionalize graphene oxide, then composites it with polyaniline, and finally reduces the graphene oxide in the composite to graphene through a reducing agent, which not only solves the phenomenon that graphene is easy to agglomerate during the polymerization process , and does not destroy the structure of graphene, the process is simple, and the functionalized graphene oxide will have a large number of negatively charged functional groups, making it easier for protonated polyaniline in acidic solution to grow uniformly on the on graphene sheets. During the preparation process, the morphology of polyaniline is regulated by controlling the conditions in the reaction process, such as temperature, amount of initiator, reaction time, etc., and the maximum utilization of polyaniline is achieved by changing the ratio of graphene, dyes and polyaniline. The specific capacitance and stability of functionalized graphene can improve the electrochemical performance of the composite, making it an excellent electrode material for supercapacitors.

Contents of the invention

The object of the present invention is to provide a preparation method and application of a dye-functionalized graphene/polyaniline composite material, so as to solve the problems of easy agglomeration of graphene and poor cycle stability of polyaniline. The prepared dye-functionalized graphene/polyaniline composite material has the characteristics of high specific capacitance and good cycle performance.

In order to realize the above-mentioned purpose of the invention, the present invention adopts following technical scheme:

A method for preparing a dye-functionalized graphene/polyaniline composite material, first preparing graphene oxide with expanded graphite; then ultrasonically dispersing dye molecules and graphene oxide uniformly, and then uniformly polymerizing aniline on the graphene oxide sheet , and finally the dye-functionalized graphene/polyaniline composite was prepared by reduction with a reducing agent.

Specifically include the following steps:

1) Preparation of graphene oxide: graphene oxide nanosheets were prepared by the improved hummers method, and dispersed in aqueous solution after stepwise centrifugation to obtain graphene oxide aqueous solution.

2) Preparation of dye-functionalized graphene oxide/polyaniline composites: Add dye to graphene oxide aqueous solution and disperse uniformly by ultrasonic, add aniline monomer to the solution in an acidic state, stir for 2 h in this state, and then select The reaction temperature was kept at a constant temperature for 30 min to obtain a dye-functionalized graphene oxide/aniline acidic mixture. Another initiator was dissolved in the acidic solution, and kept at a selected temperature for 30 min to obtain an acidic solution of the initiator. After mixing the two evenly, react at a selected temperature for 4 h to 96 h, wash and dry to obtain the dye-functionalized graphene oxide/polyaniline composite material.

In step 2), the dyes used are one or more of triphenyl blue, amino black, acid orange, amaranth, malachite green and tetraphenylporphyrin tetrasulfonic acid.

In step 2), in the dye-functionalized graphene oxide/aniline acidic mixture, the mass ratio of the dye to aniline is 1:100~10:100, and the mass ratio of graphene oxide to aniline is 1:100~20: 100.

In step 2), the selected reaction temperature is: -5°C~50°C.

In step 2), one of HCl, H ₂ SO ₄ , H ₃ PO ₄ or HNO ₃ is used as the acid in the acid state and in the acid solution; the concentration of the acid is: 0.2-3.0 mol/L.

In step 2), the initiator is selected to be one or more of ammonium persulfate, potassium persulfate, sodium persulfate, H ₂ O ₂ /FeCl ₂ or K ₂ CrO ₄ .

In step 2), the molar ratio of the initiator to the aniline monomer is 4:1~1:4.

3) Preparation of dye-functionalized graphene/polyaniline composite material: uniformly disperse the above-mentioned dye-functionalized graphene oxide/polyaniline composite material into an aqueous solution, then add a reducing agent, react at 90 °C for 12 h, and cool to room temperature Finally, the dye-functionalized graphene/polyaniline composite was obtained after washing and drying with deionized water.

In step 3), the reducing agent is selected from one or more of sodium borohydride, hydrazine hydrate, sodium hypophosphite, and ammonia water.

The application of the above-mentioned dye-functionalized graphene/polyaniline composite material in the preparation of supercapacitor electrode materials.

The beneficial effects of the present invention are:

1) The present invention uses aniline, dyes, and expanded graphite as raw materials, and utilizes the conjugation of dye molecules and graphene oxide to prevent the agglomeration of graphene oxide, and after graphene is functionalized, polyaniline is easier to grow uniformly on graphite oxide On the ene sheet, the graphene oxide was reduced to graphene by the reduction of the reducing agent, and the dye-functionalized graphene/polyaniline composite material was obtained.

2) The dye-functionalized graphene/polyaniline composite material prepared by the present invention has excellent electrochemical properties, which improves the shortcomings of graphene, such as easy agglomeration and poor dispersion during use, and improves the charging and discharging process of polyaniline The shortcomings of medium stability, and improve its specific capacitance, and make the functionalization process simple and easy, it can be used as an ideal electrode material for supercapacitors.

Description of drawings

Fig. 1 is the SEM picture of the Quli benzene blue functionalized graphene/polyaniline composite material prepared by the embodiment of the present invention 1;

Fig. 2 is the charge-discharge curve under the different current densities of the Quli benzene blue functionalized graphene/polyaniline composite material prepared by embodiment 1 of the present invention;

Fig. 3 is the SEM picture of the tetraphenylporphyrin tetrasulfonic acid functionalized graphene/polyaniline composite material prepared by the embodiment of the present invention 2;

Fig. 4 is the charge-discharge curve at 1 A/g of the tetraphenylporphyrin tetrasulfonic acid functionalized graphene/polyaniline composite material prepared by the embodiment of the present invention 2;

Fig. 5 is the stability curve of the malachite green functionalized graphene/polyaniline composite material prepared in Example 5 of the present invention after 2000 charge and discharge cycles.

Fig. 6 is the charge-discharge curve of the amino black functionalized graphene/polyaniline composite material prepared in Example 6 of the present invention at a current density of 1 A/g.

detailed description

1) Graphene oxide nanosheets were prepared by the improved Hummers method, and dispersed in aqueous solution after stepwise centrifugation to obtain graphene oxide aqueous solution.

2) Preparation of dye-functionalized graphene oxide/polyaniline composites: Add dye to graphene oxide aqueous solution and disperse uniformly by ultrasonic, add aniline monomer to the solution in an acidic state, stir for 2 h in this state, and then select The dye-functionalized graphene oxide/aniline acid mixture was obtained by incubating at a certain reaction temperature for 30 min. Another initiator was dissolved in the acidic solution, and kept at the selected reaction temperature for 30 min to obtain the acidic solution of the initiator. After mixing the acidic solution of the initiator with the dye-functionalized graphene oxide/aniline acidic mixture, the selected React at a certain reaction temperature for 4 h to 96 h, wash and dry to obtain the dye-functionalized graphene oxide/polyaniline composite material.

The above-mentioned dyes are one or more of Congo red, triphenyl blue, methylene blue, amino black, and tetraphenylporphyrin tetrasulfonic acid.

In the above dye-functionalized graphene oxide/aniline acidic mixture, the mass ratio of dye to aniline is 1:100~10:100, preferably 4:100~5:100; the mass ratio of graphene oxide to aniline is 1:100 ~20:100, preferably 5:100~10:100.

The selected reaction temperature above is: -5°C~50°C, preferably 0°C~5°C.

One of HCl, H ₂ SO ₄ , H ₃ PO ₄ or HNO ₃ is used as the acid in the above acid state and acid solution. Wherein the acid concentration is: 0.2~3.0 mol/L, preferably 1 mol/L~2 mol/L.

The above-mentioned initiator is selected from one or more of ammonium persulfate, potassium persulfate, sodium persulfate, H ₂ O ₂ /FeCl ₂ or K ₂ CrO ₄ .

The above-mentioned initiator: the molar ratio of aniline is 4:1~1:4, preferably 1:1~1:2.

3) Preparation of dye-functionalized graphene/polyaniline composite material: uniformly disperse the above-mentioned dye-functionalized graphene oxide/polyaniline composite material into an aqueous solution, then add a reducing agent, react at 90 °C for 12 h, and cool to room temperature Finally, the dye-functionalized graphene/polyaniline composite was obtained after washing and drying with deionized water.

The selection of the above-mentioned reducing agent is one or more of sodium borohydride, hydrazine hydrate, sodium hypophosphite, and ammonia water.

(4) Electrode preparation: The electrode was prepared by the tablet method. Stainless steel mesh was used as the current collector, acetylene black was used as the conductive agent, and 5 wt.% polytetrafluoroethylene was used as the binder. The composite material, acetylene black, polytetrafluoroethylene Ethylene was mixed and ground according to the mass ratio of 85:10:5 until it was ground into flakes, and the flakes were cut into a shape of 1 cm × 1 cm; then the cut flakes were placed between two stainless steel meshes, placed Under the tablet press, under the pressure of 10 MPa, hold the pressure for 1 min to obtain the working electrode;

(5) Electrochemical performance test: The electrode test system adopts a three-electrode system, and the sheet-shaped electrode is regarded as a working electrode, and then placed in the electrolyte together with the counter electrode and the reference electrode for testing through the electrochemical workstation. Dye-functionalized graphite Electrochemical properties of vinyl/polyaniline composites.

The use of the dye-functionalized graphene/polyaniline composite material of the present invention is to use it as an electrode material for a supercapacitor.

The following are several specific embodiments of the invention to further illustrate the present invention. All equivalent changes and modifications made according to the patent scope of the present invention shall fall within the scope of the present invention.

Example 1

(1) The graphene oxide prepared by the improved Hummers method was centrifuged step by step and ultrasonically dispersed to obtain a uniform dispersion with a solid content of 3.17 mg/mL. Take 34 mL (0.1081 g) of the graphene oxide dispersion at 50 mL beaker.

(2) Take 0.04325 g of Trinyl blue and add it to the above graphene oxide solution, ultrasonically disperse it for 1 h, add 0.69 mL of water and 4.4 mL of concentrated sulfuric acid to make the concentration of H ₂ SO ₄ in the solution 2 mol/L, and then Add 0.91 mL of aniline monomer, stir for 2 h, and incubate at 5 °C for 30 min.

(3) Another 4.564 g of ammonium persulfate was added to 10 mL of 2 mol/L sulfuric acid, and after the dissolution was complete, it was incubated at 0 °C for 30 min.

(4) Slowly add the solution in (3) into the solution in (2), mix well and react at 0 °C for 48 h. Wash with deionized water to pH = 7, and dry at 60 °C to constant weight to obtain Quliben blue functionalized graphene oxide/polyaniline composite. Weigh 400 mg of the complex into 200 mL of water, ultrasonically disperse for 1 h, add 0.8 mL of hydrazine hydrate, reduce at 90 °C for 12 h, wash with deionized water to pH = 7, and dry at 60 °C to constant weight. Its SEM picture is shown in accompanying drawing 1, shows that the polyaniline in the composite material grows uniformly on the graphene sheet, and the agglomeration phenomenon of graphene does not take place. The electrochemical performance test results of the obtained Quli benzene blue functionalized graphene/polyaniline composite material show that the discharge specific capacitance of the electrode material can reach 665 F/g at a current density of 1 A/g. Its charge and discharge curves at different current densities are shown in Figure 2.

Example 2

(1) The graphene oxide prepared by the improved Hummers method was centrifuged step by step and ultrasonically dispersed to obtain a uniform dispersion with a solid content of 3.17 mg/mL. Take 34 mL (0.1081 g) of the graphene oxide dispersion in in a 50 mL beaker.

(2) Add 0.04325 g of tetraphenylporphyrin tetrasulfonic acid into the above graphene oxide solution, ultrasonically disperse for 1 h, add 1.6 mL of water and 3.4 mL of hydrochloric acid to make the concentration of HCl in the solution 1 mol/L, and then Add 0.91 mL of aniline monomer, stir for 2 h, and incubate at 0 °C for 30 min.

(3) Another 2.282 g of ammonium persulfate was added to 10 mL of 1 mol/L dilute hydrochloric acid, and after the dissolution was complete, it was incubated at 0 °C for 30 min.

(4) Slowly add the solution in (3) into the solution in (2), mix well and react at 0 °C for 24 h. Wash with deionized water to pH = 7, and dry at 60 °C to constant weight to obtain tetraphenylporphyrin tetrasulfonic acid functionalized graphene oxide/polyaniline composites. Weigh 400 mg of the complex into 200 mL of water, ultrasonically disperse for 1 h, add 0.8 mL of hydrazine hydrate, reduce at 90 °C for 12 h, wash with deionized water to pH = 7, and dry at 60 °C to constant weight. Its SEM picture is shown in Figure 3. It can be seen that the graphene sheets in the composite material are uniformly dispersed without agglomeration, and polyaniline grows uniformly on the graphene surface without the formation of homopolymers. The electrochemical performance test results of the obtained tetraphenylporphyrin tetrasulfonic acid functionalized graphene/polyaniline composite material show that the discharge specific capacitance of the electrode material can reach 686 F/g at a current density of 1 A/g (as shown in Fig. 4).

Example 3

1) The graphene oxide prepared by the improved Hummers method was centrifuged step by step and ultrasonically dispersed to obtain a uniform dispersion with a solid content of 3.17 mg/mL. Take 34.5 mL (0.1094 g) of the graphene oxide dispersion in mL beaker.

(2) Add 0.0547 g of tetraphenylporphyrin tetrasulfonic acid into the above graphene oxide solution, ultrasonically disperse for 1 h, add 1.19 mL of water and 3.4 mL of hydrochloric acid to make the concentration of HCl in the solution 1 mol/L, and then Add 0.91 mL of aniline monomer, stir for 2 h, and incubate at 5 °C for 30 min.

(3) Another 2.282 g of potassium persulfate was added to 10 mL of 2 mol/L dilute hydrochloric acid, and after complete dissolution, it was incubated at 5 °C for 30 min.

(4) Slowly add the solution in (3) to the solution in (2), mix well and react at 0 °C for 12 h. Wash with deionized water to pH = 7, and dry at 60 °C to constant weight to obtain tetraphenylporphyrin tetrasulfonic acid functionalized graphene oxide/polyaniline composites. Weigh 400 mg of the complex into 200 mL of water, ultrasonically disperse for 1 h, add 0.8 mL of sodium borohydride, reduce at 90 °C for 12 h, wash with deionized water to pH = 7, and dry at 60 °C to constant weight. The electrochemical performance test results of the obtained tetraphenylporphyrin tetrasulfonic acid functionalized graphene/polyaniline composite material show that the discharge specific capacitance of the electrode material can reach 580 F/g at a current density of 1 A/g.

Example 4

(1) The graphene oxide prepared by the improved Hummers method was centrifuged step by step and ultrasonically dispersed to obtain a uniform dispersion with a solid content of 3.17 mg/mL. Take 35.7 mL (0.1134 g) of the graphene oxide dispersion in in a 50 mL beaker.

(2) Add 0.0907 g of amaranth into the above graphene oxide solution, ultrasonically disperse for 1 h, add 2.27 mL of concentrated nitric acid to make the concentration of HNO ₃ in the solution 1 mol/L, then add 0.91 mL of aniline monomer, Stir for 2 h and incubate at 0 °C for 30 min.

(3) Another 2.381 g of sodium persulfate was added into 10 mL of 1 mol/L nitric acid, and after the dissolution was complete, it was incubated at 0 °C for 30 min.

(4) Slowly add the solution in (3) into the solution in (2), mix well and react at 0 °C for 72 h. Wash with deionized water to pH = 7, and dry at 60 °C to constant weight to obtain Congo red functionalized graphene oxide/polyaniline composite. Weigh 400 mg of the complex into 200 mL of water, ultrasonically disperse for 1 h, add 0.8 mL of hydrazine hydrate, reduce at 90 °C for 12 h, wash with deionized water to pH = 7, and dry at 60 °C to constant weight. The electrochemical performance test results of the obtained amaranth functionalized graphene/polyaniline composite material show that the discharge specific capacitance of the electrode material can reach 630F/g at a current density of 1 A/g.

Example 5

1) The graphene oxide prepared by the improved Hummers method was centrifuged step by step and ultrasonically dispersed to obtain a uniform dispersion with a solid content of 3.17 mg/mL. Take 17.25 mL (0.0547 g) of the graphene oxide dispersion in mL beaker.

(2) Add 0.0547 g of malachite green to the above graphene oxide solution, ultrasonically disperse for 1 h, add 16.3 mL of water and 5.54 mL of concentrated nitric acid to make the concentration of HNO ₃ in the solution 2 mol/L, and then add 0.91 mL aniline monomer, stirred for 2 h, and incubated at 0 °C for 30 min.

(3) Another 2.381 g of sodium persulfate was added into 10 mL of 1 mol/L nitric acid, and after the dissolution was complete, it was incubated at 0 °C for 30 min.

(4) Slowly add the solution in (3) into the solution in (2), mix well and react at 0 °C for 24 h. Washing with deionized water to pH = 7, drying at 60 °C to constant weight to obtain malachite green functionalized graphene oxide/polyaniline composites. Weigh 400 mg of the complex into 200 mL of water, ultrasonically disperse for 1 h, add 0.8 mL of ammonia water, reduce at 90 °C for 12 h, wash with deionized water to pH = 7, and dry at 60 °C to constant weight. The electrochemical performance test results of the obtained malachite green functionalized graphene/polyaniline composite material show that the discharge specific capacitance of the electrode material can reach 544F/g at a current density of 1 A/g. After 2000 charge-discharge cycles, its specific capacitance still has a retention rate of 100%. As shown in Figure 5.

Example 6

1) The graphene oxide prepared by the improved Hummers method was centrifuged step by step and ultrasonically dispersed to obtain a uniform dispersion with a solid content of 3.17 mg/mL. Take 34.5 mL (0.1094 g) of the graphene oxide dispersion in mL beaker.

(2) Add 0.0547 g of amino black to the above graphene oxide solution, ultrasonically disperse for 1 h, add 2.13 mL of water and 2.46 mL of concentrated phosphoric acid to make the concentration of H ₃ PO ₄ in the solution 1 mol/L, then add 0.91 mL of aniline monomer, stirred for 2 h, and incubated at 0 °C for 30 min.

(3) Another 1.942 g K ₂ CrO ₄ was added into 10 mL of 1 mol/L phosphoric acid, and after the dissolution was complete, it was incubated at 0 °C for 30 min.

(4) Slowly add the solution in (3) into the solution in (2), mix well and react at 0 °C for 48 h. Wash with deionized water to pH = 7, and dry to constant weight at 60 °C to obtain amino black functionalized graphene oxide/polyaniline composites. Weigh 400 mg of the complex into 200 mL of water, ultrasonically disperse for 1 h, add 0.8 mL of sodium hypophosphite, reduce at 90 °C for 12 h, wash with deionized water to pH = 7, and dry at 60 °C to constant weight. The electrochemical performance test results of the obtained amino black functionalized graphene/polyaniline composite material show that the discharge specific capacitance of the electrode material can reach 589F/g at a current density of 1 A/g, as shown in Figure 6.

The above descriptions are only preferred embodiments of the present invention, and all equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope of the present invention.

Claims (10)

1. a kind of preparation method of dyefunctionalized grapheme/polyaniline composite material, it is characterised in that comprise the following steps：

1）The preparation of graphene oxide：Stannic oxide/graphene nano piece is prepared using improved Hummers methods, deionization is dispersed to Graphene oxide water solution is obtained in water；

2）The preparation of dyefunctionalized graphene oxide/polyaniline composite material：

1. dyestuff is added into ultrasonic disperse in graphene oxide water solution uniformly, makes solution add aniline list under acid state Body, stirs be incubated 30 min under selected reaction temperature after 2 h in this case, obtain dyefunctionalized graphene oxide/aniline Acid mixed solution；

2. weigh a certain amount of initiator to be dissolved in acid solution, be incubated 30 min under selected reaction temperature, obtain initiator Acid solution；

3. after initiator acid solution is well mixed with dyefunctionalized graphene oxide/aniline acid mixed solution, selected The h of 4 h ~ 96 is reacted under reaction temperature, after the completion of reaction, washing is dried to obtain dyefunctionalized graphene oxide/polyaniline and is combined Material；

3）The preparation of dyefunctionalized grapheme/polyaniline composite material：By above-mentioned dyefunctionalized graphene oxide/polyaniline Composite is dispersed into the aqueous solution, adds reducing agent, and 12 h are reacted at 90 DEG C, are cooled to after room temperature, spend from Sub- water washing obtains dyefunctionalized grapheme/polyaniline composite material after drying.

2. the preparation of dyefunctionalized grapheme/polyaniline composite material according to claim 1, it is characterised in that：Step Rapid 2）In dyestuff used it is blue for bent sharp benzene, amino black, acid orange, amaranth, malachite green, one kind of tetraphenylporphyrin tetrasulfonic acid Or it is a variety of.

3. the preparation of dyefunctionalized grapheme/polyaniline composite material according to claim 1, it is characterised in that：Step Rapid 2）In the dyefunctionalized graphene oxide/aniline acid mixed solution, the mass ratio of dyestuff and aniline is 1:100~10: 100, the mass ratio of graphene oxide and aniline is 1:100~20:100.

4. the preparation of dyefunctionalized graphene oxide/polyaniline composite material according to claim 1, its feature exists In：The step 2）In, selected reaction temperature is：-5℃~50℃.

5. the preparation of dyefunctionalized graphene oxide/polyaniline composite material according to claim 1, its feature exists In：The step 2）1. in acid state and 2. in acid solution in acid use HCl, H₂SO₄、H₃PO₄Or HNO₃In One kind；Acid concentration is：0.2~3.0 mol/L.

6. the preparation of dyefunctionalized graphene oxide/polyaniline composite material according to claim 1, its feature exists In：Step 2）In, initiator is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, H₂O₂/FeCl₂Or K₂CrO₄。

7. the preparation of dyefunctionalized grapheme/polyaniline composite material according to claim 2, it is characterised in that：Institute State step 2）In, the mol ratio of initiator and aniline monomer is 4:1~1:4.

8. the preparation of dyefunctionalized grapheme/polyaniline composite material according to claim 1, it is characterised in that：Institute State step 3）In, reducing agent is sodium borohydride, hydrazine hydrate, sodium hypophosphite, the one or more in ammoniacal liquor.

9. a kind of dyefunctionalized grapheme/polyaniline composite material prepared such as claim 1 ~ 8 either method.

10. a kind of application of dyefunctionalized grapheme/polyaniline composite material as claimed in claim 9, it is characterised in that： For preparing electrode material for super capacitor.