CN103224704A - Preparation method for polyaniline/polypyrrole binary composite nanotube - Google Patents
Preparation method for polyaniline/polypyrrole binary composite nanotube Download PDFInfo
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- CN103224704A CN103224704A CN2013101390984A CN201310139098A CN103224704A CN 103224704 A CN103224704 A CN 103224704A CN 2013101390984 A CN2013101390984 A CN 2013101390984A CN 201310139098 A CN201310139098 A CN 201310139098A CN 103224704 A CN103224704 A CN 103224704A
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Abstract
The invention belongs to the preparation field of high value addition of inorganic non-metallic minerals and high performance of nano materials. Firstly, a rod-shaped silicate clay is used as a core body and a pore-forming agent is added to process the rod-shaped silicate clay; then, aniline and pyrrole monomers are added to carry out oxidative polymerization, so as to prepare a silicate clay/polyaniline/ polypyrrole composite material; and finally, the silicate clay template is dissolved and removed by using a mixed acid to prepare the polyaniline/polypyrrole composite nanotubes. The polyaniline/polypyrrole composite material with high specific capacitance and high conductivity is prepared by the invention. The specific surface area and pore volume of the silicate clay are increased by treating the silicate clay with the pore-forming agent, thereby facilitating monomolecular adsorption of aniline or pyrrole to the surface of the silicate clay, formation of a core-shell structure, and formation of the nanotubes after the template is removed. The mixed acid is beneficial to rapidly remove the silicate clay template. Natural one-dimensional rod-shaped or fiber-shaped silicate clay which is easily available in raw materials and low in cost is selected as the template.
Description
Technical field
The present invention relates to a kind of is the polyaniline/polypyrrole nanotube preparation method of template with natural bar-shaped or fibrous silicate clay, belongs to the high added valueization of inorganic non-metallic mineral and the high performance preparation field of nano material.
Background technology
Conductive polymers, especially polyaniline and polypyrrole have advantage such as synthetic convenient, high conductivity and fake capacitance energy storage characteristic and are used to ultracapacitor, electromagnetic wave shielding and numerous areas such as antistatic.In general, the performance of material and himself structure and pattern are closely related.Polyaniline and polypyrrole have been widely used in the electrical condenser energy storage, are one of significant parameter of estimating capacitor performance than electric capacity, and bigger more than electric capacity, its energy-storage property is good more.Yet the conductive polymers great majority that are applied to electrical condenser at present are single polyaniline or polypyrrole.The conductivity of polypyrrole is better than polyaniline, and than polypyrrole, polyaniline but has higher ratio electric capacity, and the polyaniline of different-shape or polypyrrole, and it is more different than electric capacity.Chinese patent CN100497761C has announced a kind of with MnO
2Nanofiber or β-MnO
2Nanotube is as template, and by the controlled polyaniline nano pipe that prepared of melting certainly of template, but this method is to have prepared polyaniline in the environment that sulfuric acid exists, and conductivity is undesirable, and cost is higher relatively and easily produce effluent containing heavy metal ions, contaminate environment.About the polypyrrole nanotube, the research report is less both at home and abroad, is carrier usually with the carbon nanotube, coats polypyrrole on its surface and prepares carbon nano-tube/poly pyrroles matrix material, and prepared conductivity of composite material can be excellent.Yet the carbon nanotube production cost is higher, and the preparation condition harshness is unfavorable for industrialization production.
Compare with the synthetic fiber, natural bar-shaped or fibrous silicate clay has advantages such as reserves are abundant, and raw material is easy to get, and is cheap, with natural bar-like silicon silicate clay is template, prepares the polyaniline/polypyrrole composite nano tube fast and has tangible competitive edge.
Summary of the invention
The object of the invention is to provide a kind of polyaniline/polypyrrole composite nano tube and preparation method thereof, has advantages such as operation is simple, production cost is low, excellent combination property.
Technical scheme of the present invention is to be nucleome with the bar-like silicon silicate clay at first, adds pore-forming material it is handled; Add aniline and pyrrole monomer then and carry out oxidative polymerization, preparation silicate clay/polyaniline/polypyrrole matrix material; Remove bar-like silicon silicate clay template with the nitration mixture dissolving at last, make the polyaniline/polypyrrole composite nano tube.
Its concrete steps are:
(1) bar-like silicon silicate clay and pore-forming material are mixed, under 100～200 ℃ of conditions, calcined 6～24 hours, then products therefrom is joined rapidly in the deionized water, mechanical stirring 0.5～2 hour;
(2) in the slurries of step 1 gained, add aniline monomer, 15～30 ℃ of hierarchy of control temperature, stir on one side, drip the oxygenant I solution that concentration is 1.0～4.0 mol on one side, reacted suction filtration 1～6 hour, wash to filtrate pH=4～5, make the compound filter cake of silicate clay/polyaniline; Again be scattered in the filter cake of gained in the deionized water, add pyrroles and doping agent, 0～10 ℃ of hierarchy of control temperature, stir on one side, continuing on one side to drip concentration is the oxygenant II solution of 1.0～4.0 mol, reacts suction filtration 0.5～3 hour, washing makes the compound filter cake of silicate clay/polyaniline/polypyrrole;
(3) the prepared compound filter cake of step 2 is scattered in H
+Volumetric molar concentration is in the mixed acid solution of 0.5～3 mol, left standstill 2～10 hours, suction filtration, wash to filtrate pH be 2～3,50～70 ℃ down dry, promptly make the polyaniline/polypyrrole composite nano tube.
As preferably, the described silicate clay of step (1) is a kind of in sepiolite, halloysite, wollastonite or the attapulgite.
As preferably, the described pore-forming material of step (1) is Neutral ammonium fluoride (NH
4F).
As preferably, the described pore-forming material of step (1) is 0.02～0.1:1 with the ratio of silicate clay quality, and the mass ratio of silicate clay and deionized water is 0.05～0.30:1.
As preferably, a kind of for in persulphate, iodate, permanganate or the iron trichloride of the described oxygenant of step (2).The binary composite nano-tube material electric property of other oxygenant preparations is good not as the performance of each embodiment.
As preferably, described aniline of step (2) and silicate clay mass ratio are 0.3～1.0:1, pyrroles and silicate clay mass ratio are 0.1～0.5:1, and the oxygenant I is 0.5～1.5:1 with the ratio of aniline mole number, and the oxygenant II is 0.5～2:1 with the ratio of pyrroles's mole number.
As preferably, the described doping agent of step (2) is a kind of in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate or the sodium stearate; Described doping agent is 0.1～0.5:1 with the ratio of pyrroles's molar mass.Doping agent can improve the conductivity of matrix material.
As preferably, the described mixed acid solution of step (3) is a kind of in hydrofluoric acid and hydrochloric acid mixed solution, hydrofluoric acid and sulfuric acid mixed solution, hydrofluoric acid and nitric acid mixing solutions or hydrofluoric acid and the phosphoric acid mixing solutions, and its component mol ratio is 1:1 in the mixed acid solution.
The invention has the beneficial effects as follows:
1. the present invention has made full use of polypyrrole superior electrical conductivity and polyaniline high specific capacitance characteristic, has prepared the polyaniline/polypyrrole binary matrix material that a kind of high specific capacitance has high conductivity concurrently.Compare with single polyaniline or polypyrrole nanotube, the prepared polyaniline/polypyrrole binary composite nano tube of the present invention has remedied the deficiency of single polyaniline nano pipe or polypyrrole nanotube aspect of performance, excellent combination property.
2. the present invention utilizes pore-forming material that silicate clay mineral is carried out pre-treatment, this has increased the specific surface area and the pore volume of silicate clay, thereby more help aniline or pyrroles's monomolecular adsorption to the silicate clay surface, more help oxypolymerization and form nucleocapsid structure, be convenient to form nanotube after removing template.
3. the silicate clay composition has Si oxide and metal oxide, and the easy dissolves silicon oxide compound of hydrofluoric acid, the easy dissolution of metals oxide compounds of inorganic acid such as hydrochloric acid, sulfuric acid and nitric acid, so the present invention adopts nitration mixture, this more helps the quick removal of silicate clay template.
4. advantages such as to select the silicate clay of natural one-dimensional rod-like or filamentary structure for use be template in the present invention, need not painstakingly synthetic, and it is abundant to have reserves, and raw material is easy to get, and is cheap greatly reduce production cost.
Description of drawings
Fig. 1 (a) is the polyaniline/polypyrrole matrix material TEM photo of comparative example 4 preparations; (b) be the attapulgite/polyaniline/polypyrrole matrix material TEM photo of embodiment 4 preparations; (c) be embodiment 4 preparation polyaniline/polypyrrole binary composite nano tube TEM photo.
Embodiment
Below in conjunction with embodiment and comparative example, the invention will be further described, but do not limit the scope of the invention:
Embodiment 1
1. 5.0 kilograms of sepiolites and 0.1 kilogram of Neutral ammonium fluoride are mixed, calcining is 24 hours under 100 ℃ of conditions, then products therefrom is joined in 16.7 kilograms of deionized waters mechanical stirring 2 hours rapidly;
2. in the slurries of step 1 gained, add 1.5 kilograms of aniline, 15 ℃ of hierarchy of control temperature, stir on one side, the liquor ferri trichloridi that it is 1.0 mol that one side drips 8.1 liters of concentration reacted suction filtration 6 hours, wash to filtrate pH=5, make the compound filter cake of sepiolite/polyaniline; Again be scattered in the filter cake of gained in the deionized water, add 0.5 kilogram of pyrroles and 0.2 kilogram of sodium laurylsulfonate, 10 ℃ of hierarchy of control temperature, stir on one side, continue on one side to drip 14.9 liters of liquor ferri trichloridis that concentration is 1.0 mol, reacted suction filtration 0.5 hour, washing makes the compound filter cake of sepiolite/polyaniline/polypyrrole;
3. the prepared matrix material of step 2 is scattered in H
+Volumetric molar concentration is in the hydrofluoric acid and salpeter solution (nitration mixture component mol ratio is 1:1, and following examples are identical) of 0.5 mol, left standstill 10 hours, suction filtration, wash to filtrate pH be 3,50 ℃ down dry, promptly make the polyaniline/polypyrrole composite nano tube.
Embodiment 2
1. 2.0 kilograms of halloysites and 0.2 kilogram of Neutral ammonium fluoride are mixed, calcining is 6 hours under 200 ℃ of conditions, then products therefrom is joined in 40.0 kilograms of deionized waters mechanical stirring 0.5 hour rapidly;
2. in the slurries of step 1 gained, add 2.0 kilograms of aniline, 30 ℃ of hierarchy of control temperature, stir on one side, the potassium permanganate solution that it is 4.0 mol that one side drips 8.0 liters of concentration reacted suction filtration 1 hour, wash to filtrate pH=4, make the compound filter cake of halloysite/polyaniline; Again be scattered in the filter cake of gained in the deionized water, add 1.0 kilograms of pyrroles and 2.3 kilograms of sodium stearate, 0 ℃ of hierarchy of control temperature, stir on one side, continue on one side to drip 1.9 liters of potassium permanganate solutions that concentration is 4.0 mol, reacted suction filtration 3 hours, washing makes the compound filter cake of halloysite/polyaniline/polypyrrole;
3. the prepared matrix material of step 2 is scattered in H
+Volumetric molar concentration is in the hydrofluoric acid and sulphuric acid soln of 1.5 mol, left standstill 2 hours, suction filtration, wash to filtrate pH be 2,70 ℃ down dry, promptly make the polyaniline/polypyrrole composite nano tube.
Embodiment 3
1. 5.0 kilograms of wollastonites and 0.3 kilogram of Neutral ammonium fluoride are mixed, calcining is 15 hours under 150 ℃ of conditions, then products therefrom is joined in 25.0 kilograms of deionized waters mechanical stirring 1 hour rapidly;
2. in the slurries of step 1 gained, add 3.25 kilograms of aniline, 22.5 ℃ of hierarchy of control temperature, stir on one side, the potassium iodate solution that it is 3.0 mol that one side drips 11.6 liters of concentration reacted suction filtration 3 hours, wash to filtrate pH=4.5, make the compound filter cake of wollastonite/polyaniline; Again be scattered in the filter cake of gained in the deionized water, add 2.0 kilograms of pyrroles and 2.9 kilograms of Sodium dodecylbenzene sulfonatees, 8 ℃ of hierarchy of control temperature, stir on one side, continue on one side to drip 9.9 liters of potassium iodate solutions that concentration is 3.0 mol, reacted suction filtration 2 hours, washing makes the compound filter cake of wollastonite/polyaniline/polypyrrole;
3. the prepared matrix material of step 2 is scattered in H
+Volumetric molar concentration is in the hydrofluoric acid and phosphoric acid solution of 1.0 mol, left standstill 6 hours, suction filtration, wash to filtrate pH be 2.5,60 ℃ down dry, promptly make the polyaniline/polypyrrole composite nano tube.
Embodiment 4
1. 5.0 kilograms of attapulgites and 0.4 kilogram of Neutral ammonium fluoride are mixed, calcining is 12 hours under 180 ℃ of conditions, then products therefrom is joined in 50.0 kilograms of deionized waters mechanical stirring 1.5 hours rapidly;
2. in the slurries of step 1 gained, add 2.5 kilograms of aniline, 20 ℃ of hierarchy of control temperature, stir on one side, the ammonium persulfate solution that it is 2.0 mol that one side drips 10.7 liters of concentration reacted suction filtration 4 hours, wash to filtrate pH=5, make the compound filter cake of attapulgite/polyaniline; Again be scattered in the filter cake of gained in the deionized water, add 1.5 kilograms of pyrroles and 1.8 kilograms of sodium laurylsulfonates, 5 ℃ of hierarchy of control temperature, stir on one side, continue on one side to drip 12.3 liters of ammonium persulfate solutions that concentration is 2.0 mol, reacted suction filtration 1.5 hours, washing makes the compound filter cake of attapulgite/polyaniline/polypyrrole;
3. the prepared matrix material of step 2 is scattered in H
+Volumetric molar concentration is in the hydrofluoric acid and hydrochloric acid soln of 1.2 mol, left standstill 5 hours, suction filtration, wash to filtrate pH be 3,65 ℃ down dry, promptly make the polyaniline/polypyrrole composite nano tube.
Comparative example 1
In comparative example 1, the step 1 among the embodiment 4 is added the pore-forming material operation remove, other processing condition are constant, and the concrete operations step is as follows:
1. 5.0 kilograms of attapulgites are joined in 50.0 kilograms of deionized waters mechanical stirring 1.5 hours;
2. in the slurries of step 1 gained, add 2.5 kilograms of aniline, 20 ℃ of hierarchy of control temperature, stir on one side, the ammonium persulfate solution that it is 2.0 mol that one side drips 10.7 liters of concentration reacted suction filtration 4 hours, wash to filtrate pH=5, make the compound filter cake of attapulgite/polyaniline; Again be scattered in the filter cake of gained in the deionized water, add 1.5 kilograms of pyrroles and 1.8 kilograms of sodium laurylsulfonates, 5 ℃ of hierarchy of control temperature, stir on one side, continue on one side to drip 12.3 liters of ammonium persulfate solutions that concentration is 2.0 mol, reacted suction filtration 1.5 hours, washing makes the compound filter cake of attapulgite/polyaniline/polypyrrole;
3. the prepared matrix material of step 2 is scattered in H
+Volumetric molar concentration is in the hydrofluoric acid and hydrochloric acid soln of 1.2 mol, left standstill 5 hours, suction filtration, wash to filtrate pH be 3,65 ℃ down dry, promptly make the polyaniline/polypyrrole composite nano tube.
Comparative example 2
In comparative example 2, the operation of the adding pyrroles among the embodiment 4 to be removed, other processing condition are constant, and the concrete operations step is as follows:
1. 5.0 kilograms of attapulgites and 0.4 kilogram of Neutral ammonium fluoride are mixed, calcining is 12 hours under 180 ℃ of conditions, then products therefrom is joined in 50.0 kilograms of deionized waters mechanical stirring 1.5 hours rapidly;
2. in the slurries of step 1 gained, add 2.5 kilograms of aniline, 20 ℃ of hierarchy of control temperature, stir on one side, the ammonium persulfate solution that it is 2.0 mol that one side drips 10.7 liters of concentration reacted suction filtration 4 hours, wash to filtrate pH=5, make the compound filter cake of attapulgite/polyaniline;
3. the prepared compound filter cake of step 2 is scattered in H
+Volumetric molar concentration is in the hydrofluoric acid and hydrochloric acid soln of 1.2 mol, left standstill 5 hours, suction filtration, wash to filtrate pH be 3,65 ℃ down dry, promptly make the polyaniline nano pipe.
Comparative example 3
In comparative example 3, the operation of the adding aniline among the embodiment 4 to be removed, other processing condition are constant, and the concrete operations step is as follows:
1. 5.0 kilograms of attapulgites and 0.4 kilogram of Neutral ammonium fluoride are mixed, calcining is 12 hours under 180 ℃ of conditions, then products therefrom is joined in 50.0 kilograms of deionized waters mechanical stirring 1.5 hours rapidly;
2. in the slurries of step 1 gained, add 1.5 kilograms of pyrroles and 1.8 kilograms of sodium laurylsulfonates, 5 ℃ of hierarchy of control temperature, stir on one side, continue to drip 12.3 liters of ammonium persulfate solutions that concentration is 2.0 mol on one side, reacted 1.5 hours, suction filtration, washing makes the compound filter cake of attapulgite/polypyrrole;
3. the prepared matrix material of step 2 is scattered in H
+Volumetric molar concentration is in the hydrofluoric acid and hydrochloric acid soln of 1.2 mol, left standstill 5 hours, suction filtration, wash to filtrate pH be 3,65 ℃ down dry, promptly make the polypyrrole nanotube.
Comparative example 4
In comparative example 4, the adding attapulgite operation among the embodiment 4 to be removed, other processing condition are constant, and the concrete operations step is as follows:
1. in 50.0 kilograms of deionized waters, add 2.5 kilograms of aniline, 20 ℃ of hierarchy of control temperature, stir on one side, the ammonium persulfate solution that it is 2.0 mol that one side drips 10.7 liters of concentration reacted 4 hours, and suction filtration washs to filtrate pH=5, makes the polyaniline filter cake; Again be scattered in the polyaniline filter cake of gained in the deionized water, add 1.5 kilograms of pyrroles and 1.8 kilograms of sodium laurylsulfonates, 5 ℃ of hierarchy of control temperature, stir on one side, continue on one side to drip 12.3 liters of ammonium persulfate solutions that concentration is 2.0 mol, reacted suction filtration 1.5 hours, washing makes the compound filter cake of polyaniline/polypyrrole;
2. the prepared compound filter cake of step 2 is scattered in H
+Volumetric molar concentration is in the hydrofluoric acid and hydrochloric acid soln of 1.2 mol, left standstill 5 hours, suction filtration, wash to filtrate pH be 3,65 ℃ down dry, promptly make the polyaniline/polypyrrole matrix material.
Polyaniline/polypyrrole binary composite nano tube performance evaluation
Below by performance test polyaniline/polypyrrole binary composite nano tube, polyaniline nano pipe and the polypyrrole nanotube performance of experiment gained are estimated, test-results is as follows.
The volume specific resistance testing method: the volume specific resistance among the embodiment is measured by the following method: in being with graduated polyacrylic ester Glass tubing, put into the 5.00g powder, with 9.81 * 10
5The pressure of Pa is pressed in composite material powder between 2 tinsels, measures 2 resistance between tinsel with universal meter, according to R
Sp=R * A/L (wherein: R
SpBe volume specific resistance, Ω cm; R is actual measurement resistance, Ω; A is the internal diameter sectional area of Glass tubing, cm
2L is the height of powder layer, cm) calculates the volume specific resistance of powder.
Than capacitance test method: with the active material (the prepared sample of embodiment and comparative example) of gained, acetylene black and polyvinyl alcohol (mass percentage concentration 4wt%) are with the 85:10:5(mass ratio) mixed even, then it is coated on the stainless (steel) wire, coated area is 1cm
2(two-sided), dry 1h under 60 ℃ is pressurize 10min under the 10MPa condition at pressure at last, makes nanometer tube combination electrode.(CHI760D, Shanghai occasion China Instr Ltd.) tests it than electric capacity on electrochemical workstation then, according to C
m=C/m=(I Δ t)/(Δ Vm), Δ V falls for putting point voltage, and Δ t is discharge time, and I is a discharging current, and m is the electrode active material quality.By table 1 as seen, contrast the ratio electric capacity and the volume specific resistance of every embodiment and comparative example, comprehensively, the polyaniline/polypyrrole binary composite nano tube excellent combination property that the present invention is prepared.
Table 1 polyaniline nano pipe, polypyrrole nanotube and binary composite nano tube performance thereof are relatively
| ? | Than electric capacity/Fg -1 | Volume specific resistance/Ω cm |
| Embodiment 1 | 130.9 | 1.8 |
| Embodiment 2 | 124.8 | 2.5 |
| Embodiment 3 | 104.7 | 3.4 |
| Embodiment 4 | 150.6 | 0.7 |
| Comparative example 1 | 70.2 | 9.8 |
| Comparative example 2 | 100.7 | 5.7 |
| Comparative example 3 | 50.8 | 3.4 |
| Comparative example 4 | 30.2 | 0.8 |
In addition, as can be seen from Figure 1, the polyaniline/polypyrrole matrix material is a bunch shape among Fig. 1 (a), and scheme (c) middle polyaniline/polypyrrole matrix material is tubular structure, in the associative list 1 performance more as can be seen, the polyaniline/polypyrrole composite nano tube of embodiment 4 preparation reaches 150.6Fg than electric capacity
-1, and the matrix material of comparative example 4 preparations has only 30.2Fg than electric capacity
-1, illustrate that the polyaniline/polypyrrole composite nano tube of the present invention's preparation has further improved the over-all properties of polyaniline/polypyrrole matrix material by the shape that changes matrix material.
Claims (9)
1. the preparation method of a polyaniline/polypyrrole binary composite nano tube is characterized in that: be nucleome with the bar-like silicon silicate clay at first, add pore-forming material it is handled; Add aniline and pyrrole monomer then and carry out oxidative polymerization, preparation silicate clay/polyaniline/polypyrrole matrix material; Remove bar-like silicon silicate clay template with the nitration mixture dissolving at last, make the polyaniline/polypyrrole composite nano tube.
2. the preparation method of polyaniline/polypyrrole binary composite nano tube according to claim 1, it is characterized in that: concrete steps are as follows:
(1) bar-like silicon silicate clay and pore-forming material are mixed, under 100～200 ℃ of conditions, calcined 6～24 hours, then products therefrom is joined rapidly in the deionized water, mechanical stirring 0.5～2 hour;
(2) in the slurries of step 1 gained, add aniline monomer, 15～30 ℃ of hierarchy of control temperature, stir on one side, drip the oxygenant I solution that concentration is 1.0～4.0 mol on one side, reacted suction filtration 1～6 hour, wash to filtrate pH=4～5, make the compound filter cake of silicate clay/polyaniline; Again be scattered in the filter cake of gained in the deionized water, add pyrroles and doping agent, 0～10 ℃ of hierarchy of control temperature, stir on one side, continuing on one side to drip concentration is the oxygenant II solution of 1.0～4.0 mol, reacts suction filtration 0.5～3 hour, washing makes the compound filter cake of silicate clay/polyaniline/polypyrrole;
(3) the prepared compound filter cake of step 2 is scattered in H
+Volumetric molar concentration is in the mixed acid solution of 0.5～3 mol, left standstill 2～10 hours, suction filtration, wash to filtrate pH be 2～3,50～70 ℃ down dry, promptly make the polyaniline/polypyrrole composite nano tube.
3. the preparation method of polyaniline/polypyrrole binary composite nano tube according to claim 2 is characterized in that: the described silicate clay of step (1) is a kind of in sepiolite, halloysite, wollastonite or the attapulgite.
4. the preparation method of polyaniline/polypyrrole binary composite nano tube according to claim 2 is characterized in that: the described pore-forming material of step (1) is Neutral ammonium fluoride (NH
4F).
5. the preparation method of polyaniline/polypyrrole binary composite nano tube according to claim 2, it is characterized in that: the described pore-forming material of step (1) is 0.02～0.1:1 with the ratio of silicate clay quality, and the mass ratio of silicate clay and deionized water is 0.05～0.30:1.
6. the preparation method of polyaniline/polypyrrole binary composite nano tube according to claim 2 is characterized in that: a kind of for in persulphate, iodate, permanganate or the iron trichloride of the described oxygenant of step (2).
7. the preparation method of polyaniline/polypyrrole binary composite nano tube according to claim 2, it is characterized in that: described aniline of step (2) and silicate clay mass ratio are 0.3～1.0:1, pyrroles and silicate clay mass ratio are 0.1～0.5:1, the oxygenant I is 0.5～1.5:1 with the ratio of aniline mole number, and the oxygenant II is 0.5～2:1 with the ratio of pyrroles's mole number.
8. the preparation method of polyaniline/polypyrrole binary composite nano tube according to claim 2, it is characterized in that: the described doping agent of step (2) is a kind of in sodium laurylsulfonate, Sodium dodecylbenzene sulfonate or the sodium stearate, and described doping agent is 0.1～0.5:1 with the ratio of pyrroles's molar mass.
9. the preparation method of polyaniline/polypyrrole binary composite nano tube according to claim 2, it is characterized in that: the described mixed acid solution of step (3) is a kind of in hydrofluoric acid and hydrochloric acid mixed solution, hydrofluoric acid and sulfuric acid mixed solution, hydrofluoric acid and nitric acid mixing solutions or hydrofluoric acid and the phosphoric acid mixing solutions, and its component mol ratio is 1:1 in the mixed acid solution.
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