CN102321254A - Preparation method for high-concentration graphene-polyaniline nanofiber composite dispersion liquid and high-concentration graphene-polyaniline nanofiber composite film - Google Patents
Preparation method for high-concentration graphene-polyaniline nanofiber composite dispersion liquid and high-concentration graphene-polyaniline nanofiber composite film Download PDFInfo
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Abstract
The invention relates to a preparation method for a high-concentration graphene-polyaniline nanofiber composite dispersion liquid and a high-concentration graphene-polyaniline nanofiber composite film. The method comprises: respectively adding graphite oxide and polyaniline nanofiber to two parts of distilled water to carry out ultrasonic dispersion to obtain a graphene oxide dispersion liquid and a polyaniline nanofiber dispersion liquid; adding the polyaniline nanofiber dispersion liquid to the graphene oxide dispersion liquid in a dropwise manner, then carrying out ultrasonic dispersion to form a composite dispersion liquid; mixing the composite dispersion liquid and a reducing agent, then carrying out the reaction under conditions of a constant temperature and ultrasonic wave to obtain the graphene-polyaniline nanofiber composite dispersion liquid; carrying out vacuum filtration for the graphene-polyaniline nanofiber composite dispersion liquid to prepare the composite film; adopting dilute acid leaching to prepare the self-supporting composite film with high conductivity. According to the method, the polyaniline nanofiber is adopted as the dispersion stabilizer for the graphene to prepare the high-concentration composite dispersion liquid, such that the problem of difficult removal of the traditional dispersing agent is solved, the synergistic effect of the composite material is easily provided. In addition, the prepared self-supporting composite film has good flexibility and high conductivity.
Description
Technical field
The invention belongs to field of material preparation, be specifically related to the preparation method of a kind of high concentration graphene-polyaniline nano fiber composite dispersion liquid and composite package.
Background technology
Since 2004 found Graphene, people generally believed that Graphene will cause revolutionary variation with its particular structure and excellent electricity, calorifics and mechanical property in various fields.Preparation method of graphene has a lot, as micromechanics peel off, chemical vapour deposition, crystal epitaxy and solvent are peeled off etc., but the Graphene poor in processability of these methods preparations has limited its large-scale application.Graphene is prepared into dispersion liquid then can improves its processibility greatly, make it can extensively be used in liquid-liquid self-assembly, vacuum filtration and prepare composite.Yet Graphene is made up of a large amount of aromatic carbon atoms, has great specific surface area, and the intensive model ylid bloom action power between layer and the layer is very easily reunited it, is difficult to obtain stable Graphene dispersion liquid.
Oxidation reduction process realizes that with being easy to the advantage of mass-producing becomes the best approach of preparation Graphene dispersion liquid with its less cost, but makes graphene oxide in the process that Graphene transforms through reductive agent, and the reunion of the Graphene that accompanies with it will take place.The graphene oxide surface has a lot of polarity oxygen-containing functional groups, like hydroxyl, carboxyl and epoxy group(ing), is easy to be dispersed in the stable dispersion liquid of formation in the polar solvent.Yet along with the carrying out of reduction reaction, the oxygen-containing functional group on the graphene film is removed gradually, separates out owing to intensive interaction graphene film between layer and the layer very easily forms coacervate, is difficult to obtain stable dispersion liquid.Though there is the investigator to adopt dispersion stabilizers such as water-soluble polymer, biomacromolecule and tensio-active agent can suppress the reunion of graphene film; Prepare stable Graphene dispersion liquid; But the existence of these dispersion agents has not only increased the complicacy of subsequent technique but also has been difficult to remove that (Langmuir 2009; 25,12030-12033).Dispersion agent remains on the graphene film, greatly reduces Graphene itself excellent light, electricity and magnetic property, has limited the application of Graphene.
Polyaniline nano fiber has the characteristic of intrinsically conducting polymer and nano material concurrently; The synergistic effect that is expected to bring into play the two as the dispersion stabilizer of Graphene prepares the excellent matrix material of bright dipping, electricity and magnetic property; Yet present preparation method can't obtain stable high concentration graphene-polyaniline composite dispersion liquid.Polyaniline is as a kind of intrinsically conducting polymer; With its cheap price, good environmental stability, unique doping dedoping mechanism and excellent electrochemical activity; Can extensively be used in fields such as transmitter, ultracapacitor, secondary cell and electromagnetic shielding, become the object that numerous investigators pay close attention to.The polyaniline distinctive molecular structure can and the π system of Graphene, remaining oxygen-containing functional group between noncovalent interactions such as pi-pi accumulation, hydrogen bond and electrostatic force take place, combination is expected to prepare a kind of novel material with photoelectric activity of excellent performance with polyaniline with Graphene.
Some investigators adopt the chemistry or the electrochemical polymerization of original position; The method of covalency or non-covalent modification and self-assembly has prepared the matrix material of graphene oxide/Graphene and polyaniline; (Carbon 2010,48,487-493 yet these matrix materials often have relatively poor processibility; ACS Nano2009,3,1745-1752; Electrochem Commun 2009,11,1158-1161).Preparation about Graphene-polyaniline composite material dispersion liquid rarely has bibliographical information; Only the people such as Shi of Tsing-Hua University study this; Adopt the Graphene dispersion liquid and the polyaniline nano fiber dispersion liquid of dialysis purifying then to prepare Graphene-polyaniline nano fiber composite dispersion liquid through physical mixed, technology is quite consuming time but dialyse early stage, very low (the ACS Nano 2010 of the dispersion liquid concentration of preparation; 4,1963-1970).The dispersion stabilization of low dispersion concentration and difference has limited the application of Graphene-polyaniline composite material.All be employed in the in-situ polymerization that carries out aniline in the dispersion liquid of graphene oxide among Chinese patent CN101781459A, CN101781458A and the CN101985517A, then obtain the matrix material of Graphene-polyaniline through reduction.This matrix material is insoluble not molten, and is difficult to be dispersed in the liquid medium, thereby processibility is relatively poor, is difficult to satisfy the application need of vacuum filtration, spraying, spin coating and liquid-technologies such as liquid self-assembly, has limited the application of matrix material.Therefore, adopt easy method to prepare stable high concentration graphene-polyaniline composite dispersion liquid and help to expand the Application Areas of Graphene.
Summary of the invention
The object of the present invention is to provide that a kind of preparation technology is simple, temperature of reaction is low, the preparation method of easy industrialization realization high concentration graphene-polyaniline nano fiber composite dispersion liquid and composite package.
For achieving the above object, the preparation method of high concentration graphene of the present invention-polyaniline nano fiber composite dispersion liquid is following:
1) preparation of graphene oxide-polyaniline nano fiber dispersion liquid
Graphite oxide and polyaniline nano fiber are added respectively in the zero(ppm) water, and obtaining stable concentration behind the ultra-sonic dispersion 2h is the graphene oxide dispersion liquid of 0.5～2mg/mL and the polyaniline nano fiber dispersion liquid that concentration is 0.1～0.3mg/mL;
Is to graphene oxide dispersion liquid in dropwise to add polyaniline nano fiber dispersion liquid at 1～4: 1 by graphene oxide than the mass ratio of polyaniline nano fiber; The pH that continues ultra-sonic dispersion 2h and regulation system is 4, and obtaining total concn is graphene oxide-polyaniline nano fiber dispersion liquid of 0.5～1mg/mL;
2) preparation of high concentration graphene-polyaniline nano fiber composite dispersion liquid
Under nitrogen protection; Graphene oxide-polyaniline nano fiber dispersion liquid is placed water bath with thermostatic control; Remain on 50～80 ℃; Dropwise add reductive agent, reaction 2～4h obtains Graphene-polyaniline nano fiber composite dispersion liquid under UW, and wherein the mass ratio of graphene oxide and reductive agent is 10: 5～9.
Described reductive agent is one or more in hydrazine, dimethylhydrazine, quadrol, Ursol D, the Peng Qinghuana.
The preparation method of high concentration graphene of the present invention-polyaniline nano fiber composite package is following:
Graphene-polyaniline nano fiber composite dispersion liquid is added vacuum filtration in the B; After treating that filtrating is drained, in B, add diluted acid, drip washing Graphene-polyaniline nano fiber composite package; After taking out oven dry, obtain the composite package that thickness is 0.5～2 μ m.
It is a kind of in Hydrogen chloride, dilute sulphuric acid, rare nitric acid, rare camphorsulfonic acid aqueous solution or the rare tosic acid aqueous solution of 0.05～1mol/L that described diluted acid adopts concentration.
The present invention is directed to present Graphene-polyaniline composite material and in application, have the shortcoming of poor in processability; Space obstacle effect and cavitation effect of ultrasonic waves by polyaniline nano fiber; Significantly suppress the agglomeration that in the Graphene conversion process, takes place by graphene oxide, prepared stable high concentrations Graphene-polyaniline nano fiber composite dispersion liquid.It is the manufacture field of support and the preparation field of matrix material that the composite dispersion liquid of this method preparation not only can extensively be used in the solvent; And used this composite dispersion liquid flexible self-supporting composite package that adopted the vacuum filtration prepared; After hydrochloric acid drip washing, the specific conductivity of this composite package specific conductivity has had significant raising.
The polyaniline nano fiber dispersion liquid is acid because the Graphene dispersion liquid is alkalescence, and the two is mixed the electrostatic balance that has destroyed former system through simple physics, can cause deposition to occur very soon, is difficult to prepare the stable composite dispersion liquid.The present invention avoids adopting the method for direct admixed graphite alkene dispersion liquid and polyaniline nano fiber dispersion liquid; But the close graphene oxide dispersion liquid of the pH value that will prepare in advance mixes with the polyaniline nano fiber dispersion liquid, prepared the composite dispersion liquid of graphene oxide-polyaniline nano fiber.Contain a large amount of oxygen-containing functional groups on the lamella of graphene oxide, conjugated structure suffers serious and destroys, lost the excellent electric property of Graphene.Through graphene oxide is reduced, prepared stable Graphene-polyaniline nano fiber dispersion liquid, so that improve its processibility the excellent performance of performance Graphene the time.
Because Graphene is made up of a large amount of aromatic carbon atoms and has extremely strong hydrophobicity, is difficult to be dispersed in the stable dispersion liquid of formation in the water.Do not regulate system pH; In the graphene oxide dispersion liquid, directly adopt the hydrazine reduction, along with the carrying out of reduction reaction, the carboxyl that has negative charge on the graphene oxide sheet is removed gradually; Electrostatic repulsion forces weakens gradually, and system occurs irreversible coacervate very soon and separates out.Though UW can suppress the reunion of graphene film to a certain extent, lack physical barrier and Coulomb repulsion effect, still be difficult to suppress fully the reunion of graphene film.Have unique molecular structure polyaniline nanofiber, can be adsorbed on the reunion that the effect of playing physical barrier on the graphene film suppresses Graphene, help obtaining stable Graphene-polyaniline nano fiber dispersion liquid.To adopting the composite package of vacuum filtration preparation, after the drip washing of employing diluted acid, increased substantially the specific conductivity of Graphene, help expanding of the application of Graphene-polyaniline composite material in fields such as energy storage and conversion, transmitter and flexible demonstrations.
The present invention prepares in the process of Graphene dispersion liquid at the auxiliary redox graphene of UW, as dispersion stabilizer, has obtained stable high concentration graphene-polyaniline nano fiber composite dispersion liquid with polyaniline nano fiber.Present method is a kind of easy method for preparing Graphene-polyaniline nano fiber composite dispersion liquid apace; The flexible self-supporting composite package that the employing vacuum filtration obtains is after diluted acid drip washing; Has higher specific conductivity; The electrode that can be widely used in ultracapacitor, solar cell, fields such as flexible display and transmitter.
Description of drawings
Fig. 1 Graphene=polyaniline nano fiber composite dispersion liquid is stable deposits the photo after 30 days.
The TEM photo of Fig. 2 Graphene-polyaniline nano fiber matrix material.
The FT-IR spectrogram of Fig. 3 Graphene (a), Graphene-polyaniline nano fiber mixture (b) and polyaniline nano fiber (c).
The flexible self-supporting Graphene of Fig. 4-polyaniline nano fiber composite package
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is done further explain.
Embodiment 1:
1) preparation of graphene oxide-polyaniline nano fiber dispersion liquid
Graphite oxide and polyaniline nano fiber are added respectively in the zero(ppm) water, and obtaining stable concentration behind the ultra-sonic dispersion 2h is the graphene oxide dispersion liquid of 1mg/mL and the polyaniline nano fiber dispersion liquid that concentration is 0.2mg/mL;
Is to graphene oxide dispersion liquid in dropwise to add the polyaniline nano fiber dispersion liquid at 3: 1 by graphene oxide than the mass ratio of polyaniline nano fiber; After adding an amount of zero(ppm) water; The pH value that continues ultra-sonic dispersion 2h and regulation system is 4, and obtaining total concn is graphene oxide-polyaniline nano fiber dispersion liquid of 0.6mg/mL;
2) preparation of high concentration graphene-polyaniline nano fiber composite dispersion liquid
Under nitrogen protection; Graphene oxide-polyaniline nano fiber composite dispersion liquid is placed water bath with thermostatic control; Remain on 55 ℃; Dropwise add the borane reducing agent sodium hydride, reaction 4h obtains Graphene-polyaniline nano fiber composite dispersion liquid under UW, and wherein the mass ratio of graphene oxide and reductive agent is 10: 6;
3) preparation of Graphene-polyaniline nano fiber composite package
Graphene-polyaniline nano fiber composite dispersion liquid is added vacuum filtration in the B; After treating that filtrating is drained, in B, adding concentration is the aqueous sulfuric acid of 0.5mol/L, drip washing Graphene-polyaniline nano fiber composite package; After taking out oven dry, obtain the composite package that thickness is 1 μ m.
Embodiment 2:
1) preparation of graphene oxide-polyaniline nano fiber dispersion liquid
Graphite oxide and polyaniline nano fiber are added respectively in the zero(ppm) water, and obtaining stable concentration behind the ultra-sonic dispersion 2h is the graphene oxide dispersion liquid of 1.5mg/mL and the polyaniline nano fiber dispersion liquid that concentration is 0.3mg/mL;
Is to graphene oxide dispersion liquid in dropwise to add the polyaniline nano fiber dispersion liquid at 4: 1 by graphene oxide than the mass ratio of polyaniline nano fiber; After adding an amount of zero(ppm) water; The pH value that continues ultra-sonic dispersion 2h and regulation system is 4, and obtaining total concn is graphene oxide-polyaniline nano fiber dispersion liquid of 0.8mg/mL;
2) preparation of high concentration graphene-polyaniline nano fiber composite dispersion liquid
Under nitrogen protection; Graphene oxide-polyaniline nano fiber dispersion liquid is placed water bath with thermostatic control; Remain on 80 ℃; Dropwise add the reductive agent Ursol D, reaction 2h obtains Graphene-polyaniline nano fiber composite dispersion liquid under UW, and wherein the mass ratio of graphene oxide and reductive agent is 10: 5;
3) preparation of Graphene-polyaniline nano fiber composite package
Graphene-polyaniline nano fiber composite dispersion liquid is added vacuum filtration in the B; After treating that filtrating is drained; In B, adding concentration is the tosic acid aqueous solution of 0.1mol/L; Drip washing Graphene-polyaniline nano fiber composite package after the taking-up oven dry, obtains the composite package that thickness is 0.5 μ m.
Embodiment 3:
1) preparation of graphene oxide-polyaniline nano fiber dispersion liquid
Graphite oxide and polyaniline nano fiber are added respectively in the zero(ppm) water, and obtaining stable concentration behind the ultra-sonic dispersion 2h is the graphene oxide dispersion liquid of 0.8mg/mL and the polyaniline nano fiber dispersion liquid that concentration is 0.2mg/mL;
Is to graphene oxide dispersion liquid in dropwise to add the polyaniline nano fiber dispersion liquid at 2: 1 by graphene oxide than the mass ratio of polyaniline nano fiber; After adding an amount of zero(ppm) water; The pH value that continues ultra-sonic dispersion 2h and regulation system is about 4, and obtaining total concn is graphene oxide-polyaniline nano fiber dispersion liquid of 0.7mg/mL;
2) preparation of high concentration graphene-polyaniline nano fiber composite dispersion liquid
Under nitrogen protection; Graphene oxide-polyaniline nano fiber dispersion liquid is placed water bath with thermostatic control; Remain on 50 ℃; Dropwise add the reductive agent dimethylhydrazine, reaction 4h obtains Graphene-polyaniline nano fiber composite dispersion liquid under UW, and wherein the mass ratio of graphene oxide and reductive agent is 10: 8;
3) preparation of Graphene-polyaniline nano fiber composite package
Graphene-polyaniline nano fiber composite dispersion liquid is added vacuum filtration in the B; After treating that filtrating is drained, in B, adding concentration is the aqueous hydrochloric acid of 1mol/L, drip washing Graphene-polyaniline nano fiber composite package; After taking out oven dry, obtain the composite package that thickness is 1.5 μ m.
Embodiment 4:
1) preparation of graphene oxide-polyaniline nano fiber dispersion liquid
Graphite oxide and polyaniline nano fiber are added respectively in the zero(ppm) water, and obtaining stable concentration behind the ultra-sonic dispersion 2h is the graphene oxide dispersion liquid of 1mg/mL and the polyaniline nano fiber dispersion liquid that concentration is 0.2mg/mL;
Is to graphene oxide dispersion liquid in dropwise to add the polyaniline nano fiber dispersion liquid at 4: 1 by graphene oxide than the mass ratio of polyaniline nano fiber; After adding an amount of zero(ppm) water; The pH value that continues ultra-sonic dispersion 2h and regulation system is about 4, and obtaining total concn is graphene oxide-polyaniline nano fiber dispersion liquid of 0.5mg/mL;
2) preparation of high concentration graphene-polyaniline nano fiber composite dispersion liquid
Under nitrogen protection; Graphene oxide-polyaniline nano fiber dispersion liquid is placed water bath with thermostatic control; Remain on 65 ℃; Dropwise add the reductive agent quadrol, reaction 3h obtains Graphene-polyaniline nano fiber composite dispersion liquid under UW, and wherein the mass ratio of graphene oxide and reductive agent is 10: 7;
3) preparation of Graphene-polyaniline nano fiber composite package
Graphene-polyaniline nano fiber composite dispersion liquid is added vacuum filtration in the B; After treating that filtrating is drained, in B, adding concentration is the aqueous nitric acid of 0.8mol/L, drip washing Graphene-polyaniline nano fiber composite package; After taking out oven dry, obtain the composite package that thickness is 1 μ m.
Embodiment 5:
1) preparation of graphene oxide-polyaniline nano fiber dispersion liquid
Graphite oxide and polyaniline nano fiber are added respectively in the zero(ppm) water, and obtaining stable concentration behind the ultra-sonic dispersion 2h is the graphene oxide dispersion liquid of 0.5mg/mL and the polyaniline nano fiber dispersion liquid that concentration is 0.1mg/mL;
Is to graphene oxide dispersion liquid in dropwise to add the polyaniline nano fiber dispersion liquid at 1: 1 by graphene oxide than the mass ratio of polyaniline nano fiber; After adding an amount of zero(ppm) water; The pH value that continues ultra-sonic dispersion 2h and regulation system is 4, and obtaining total concn is graphene oxide-polyaniline nano fiber dispersion liquid of 0.1mg/mL;
2) preparation of high concentration graphene-polyaniline nano fiber composite dispersion liquid
Under nitrogen protection; Graphene oxide-polyaniline nano fiber dispersion liquid is placed water bath with thermostatic control; Remain on 70 ℃; The mixture that dropwise adds hydrazine reducing agent and Ursol D, reaction 3h obtains Graphene-polyaniline nano fiber composite dispersion liquid under UW, and wherein the mass ratio of graphene oxide and reductive agent is 10: 9;
3) preparation of Graphene-polyaniline nano fiber composite package
Graphene-polyaniline nano fiber composite dispersion liquid is added vacuum filtration in the B; After treating that filtrating is drained; In B, adding concentration is the camphorsulfonic acid aqueous solution of 0.3mol/L; Drip washing Graphene-polyaniline nano fiber composite package after the taking-up oven dry, obtains the composite package that thickness is 2 μ m.
Embodiment 6:
1) preparation of graphene oxide-polyaniline nano fiber dispersion liquid
Graphite oxide and polyaniline nano fiber are added respectively in the zero(ppm) water, and obtaining stable concentration behind the ultra-sonic dispersion 2h is the graphene oxide dispersion liquid of 2mg/mL and the polyaniline nano fiber dispersion liquid that concentration is 0.3mg/mL;
Is to graphene oxide dispersion liquid in dropwise to add the polyaniline nano fiber dispersion liquid at 2: 1 by graphene oxide than the mass ratio of polyaniline nano fiber; After adding an amount of zero(ppm) water; The pH value that continues ultra-sonic dispersion 2h and regulation system is 4, and obtaining total concn is graphene oxide-polyaniline nano fiber dispersion liquid of 1mg/mL;
2) preparation of high concentration graphene-polyaniline nano fiber composite dispersion liquid
Under nitrogen protection; Graphene oxide-polyaniline nano fiber dispersion liquid is placed water bath with thermostatic control; Remain on 75 ℃; The mixture that dropwise adds reductive agent dimethylhydrazine, Ursol D and Peng Qinghuana, reaction 2h obtains Graphene-polyaniline nano fiber composite dispersion liquid under UW, and wherein the mass ratio of graphene oxide and reductive agent is 10: 7.5;
3) preparation of Graphene-polyaniline nano fiber composite package
Graphene-polyaniline nano fiber composite dispersion liquid is added vacuum filtration in the B; After treating that filtrating is drained; In B, adding concentration is the tosic acid aqueous solution of 0.05mol/L; Drip washing Graphene-polyaniline nano fiber composite package after the taking-up oven dry, obtains the composite package that thickness is 0.5 μ m.
Outstanding feature of the present invention is:
(1) can prepare high density (＞0.5mg/mL) Graphene-polyaniline nano fiber composite dispersion liquid, and dispersion stabilization is better, can stablize and place more than 30;
(2) this composite dispersion liquid had good snappiness through the self-supporting composite package of vacuum filtration preparation; After adopting diluted acid drip washing; Increased substantially the specific conductivity of composite package, made it in wide application prospects of field tool such as self-supporting electrode, flexible display and transmitters;
(3) pattern is clear and definite polyaniline nano fiber is incorporated in the preparation process of matrix material, has realized that the height of matrix material pattern is controlled;
(4) UW can make Graphene and polyaniline nano fiber be uniformly dispersed, and therefore in the Graphene-polyaniline nano fiber composite package of the preparation of preparation, the two has realized excellent contact;
(5) preparing method's desired reaction temperature of the present invention is low, and safety is easy to operate, technological process is simple and easy to do, be convenient to amplify production, low operation cost;
Graphene-polyaniline nano fiber the composite dispersion liquid of the high-concentration stable of the present invention's preparation has improved the processibility of Graphene-polyaniline nano fiber matrix material significantly; Make it can be widely used in spin coating, drip and to be coated with, to spray; Liquid-liquid self-assembly and prepare composite, help Graphene-polyaniline composite material device.Adopt the graphene composite material of the present invention's preparation not only to have Graphene and polyaniline excellent properties separately, and can give full play to the collaborative effectiveness of Graphene and polyaniline.Therefore, the present invention has extremely important actual application value.
The present invention is employed in and introduces polyaniline nano fiber in the reduction process of graphene oxide as dispersion stabilizer, after the Graphene of preparing-polyaniline nano fiber composite dispersion liquid leaves standstill 30 days, and stable homogeneous (see figure 1) still.Can find out that from Fig. 2 TEM photo polyaniline nano fiber is dispersed on the graphene film, play the effect that Graphene is reunited that suppresses.From Fig. 3, can find out the charateristic avsorption band that has polyaniline nano fiber and Graphene in the ir spectra of Graphene-polyaniline nano fiber mixture, prove that the two is present in the matrix material.Graphene-polyaniline nano fiber composite dispersion liquid is adopted the self-supporting composite conductive film of vacuum filtration preparation; 180 ° of several of cyclic bending; Still have good snappiness (Fig. 4), specific conductivity can be used for the ultracapacitor of self-supporting, the electrode of solar cell up to 1200S/m behind weak acid scrubbing; Field such as flexible display and transmitter, the application of having expanded Graphene.
Claims (4)
1. the preparation method of high concentration graphene-polyaniline nano fiber composite dispersion liquid is characterized in that:
1) preparation of graphene oxide-polyaniline nano fiber dispersion liquid
Graphite oxide and polyaniline nano fiber are added respectively in the zero(ppm) water, and obtaining stable concentration behind the ultra-sonic dispersion 2h is the graphene oxide dispersion liquid of 0.5～2mg/mL and the polyaniline nano fiber dispersion liquid that concentration is 0.1～0.3mg/mL;
Is to graphene oxide dispersion liquid in dropwise to add polyaniline nano fiber dispersion liquid at 1～4: 1 by graphene oxide than the mass ratio of polyaniline nano fiber; The pH that continues ultra-sonic dispersion 2h and regulation system is 4, and obtaining total concn is graphene oxide-polyaniline nano fiber dispersion liquid of 0.5～1mg/mL;
2) preparation of high concentration graphene-polyaniline nano fiber composite dispersion liquid
Under nitrogen protection; Graphene oxide-polyaniline nano fiber dispersion liquid is placed water bath with thermostatic control; Remain on 50～80 ℃; Dropwise add reductive agent, reaction 2～4h obtains Graphene-polyaniline nano fiber composite dispersion liquid under UW, and wherein the mass ratio of graphene oxide and reductive agent is 10: 5～9.
2. the preparation method of high concentration graphene according to claim 1-polyaniline nano fiber composite dispersion liquid is characterized in that: described reductive agent is one or more in hydrazine, dimethylhydrazine, quadrol, Ursol D, the Peng Qinghuana.
3. one kind is adopted the high concentration graphene-polyaniline nano fiber composite dispersion liquid of claim 1 preparation to prepare the method for composite package; It is characterized in that: Graphene-polyaniline nano fiber composite dispersion liquid is added vacuum filtration in the B; After treating that filtrating is drained, in B, add diluted acid, drip washing Graphene-polyaniline nano fiber composite package; After taking out oven dry, obtain the composite package that thickness is 0.5～2 μ m.
4. the preparation method of high concentration graphene according to claim 3-polyaniline nano fiber composite package is characterized in that: it is a kind of in Hydrogen chloride, dilute sulphuric acid, rare nitric acid, rare camphorsulfonic acid aqueous solution or the rare tosic acid aqueous solution of 0.05～1mol/L that described diluted acid adopts concentration.
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