CN104112603B - Polypyrrole-titanium dioxide or titanium nitride-polyaniline coaxial three-layer nanotube array composite material, and preparation method and application thereof - Google Patents
Polypyrrole-titanium dioxide or titanium nitride-polyaniline coaxial three-layer nanotube array composite material, and preparation method and application thereof Download PDFInfo
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- CN104112603B CN104112603B CN201410262000.9A CN201410262000A CN104112603B CN 104112603 B CN104112603 B CN 104112603B CN 201410262000 A CN201410262000 A CN 201410262000A CN 104112603 B CN104112603 B CN 104112603B
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Abstract
The invention provides a coaxial three-layer nanotube array composite material. The coaxial three-layer nanotube array composite material comprises a titanium dioxide or titanium nitride nanotube array frame, a polypyrrole nanotube formed through polymeric deposition at the outer wall surface of the frame, and a polyaniline nanotube formed through polymeric deposition at the inner wall surface of the frame. The invention also provides a preparation method of the coaxial three-layer nanotube array composite material and an electrochemical energy storage application of the coaxial three-layer nanotube array composite material. The composite material is prepared by taking a titanium dioxide or titanium nitride nanotube as the frame, the frame is of a hollow structure, has uniform tube spacing and can absorb volume contraction and expansion caused when a conductive polymer is charged and discharged, and the circulating life of an electrode material is prolonged; the multi-gap hollow tubular structure enables polyaniline and polypyrrole to be fully contacted with a doping agent electrolyte, such that ion diffusion and charge transfer are facilitated; and the composite material comprises P-type doped characteristic polypyrrole and n-type doped characteristic polypyrrole at the same time and fully utilizes anions and cations in a solution so as to obtain a super capacitor electrode material with high specific capacitance and good circulating stability.
Description
Technical field
The invention belongs to electrochemical material field, is related to a kind of coaxial three layers of nanotube array composite material, more particularly to
A kind of polypyrrole-titanium dioxide-the polyaniline or polypyrrole-titanium nitride-polyaniline of coaxial three layers of nano-tube array structure is combined
Material, is that one kind is received by titanium dioxide or titanium nitride nano cannon born frame, N-shaped doping conductive polymer polypyrrole more specifically
Mitron, p-type doping conductive polymer polyanaline nanotube ordered fabrication form coaxial three layers of nanometer tube composite materials, further relate to this
The preparation method of coaxial three layers of nanotube array composite material and the application in electrochemical energy storage field.
Background technology
Ultracapacitor is a kind of novel energy storage apparatus of performance between dielectric capacitor and battery, the device tool
Have the advantages that charge-discharge velocity is fast, specific capacity is big, have extended cycle life, extensively application and portable electric appts, hybrid power vapour
The fields such as car.Electrode material is the most key part of ultracapacitor, is also the principal element for determining its performance, therefore is developed
Electrode material with excellent storing up electricity performance is most crucial content in ultracapacitor research.
Conducting polymer is the important electrode material for super capacitor of a class, and it is accurate that its storing up electricity performance mostlys come from faraday
Electric capacity.Conducting polymer has big conjugated pi system also known as conducting polymer, in this kind of macromolecular structure, by handss such as doping
Section, realizes the transfer of electric charge and conduction is realized in flowing in the form of pi-electron in conjugated pi system.Common conducting polymer has：
Polyacetylene, polypyrrole, polyaniline, polythiophene and its derivant etc..Electric polypyrrole is typical p-type doping conducting polymer,
Conventional anion doped dose has lithium perchlorate, sulfonic dopants, mineral acid dopant etc., and polypyrrole has good chemistry
Stability, doping after high conductivity, be readily synthesized, pattern in regulation and control the advantages of.Bronsted acid of the electrically conductive polyaniline with uniqueness/
Cation doping mechanism, conventional cation acid dopant is the acid of various organic protons and inanimate matter acid.Polyaniline conductivity is good,
There is monomer low price, high charge density, be one of most potential kind in conducting polymer composite.
The polypyrrole active material of introducing p-type doping simultaneously is lived with the polyaniline of N-shaped doping in same electrode material for super capacitor
Property material, during capacitor charging/discharging, two kinds of active materials simultaneously participate in the charge transfer process of ion doping, can be fully
Using zwitterion in electrolyte, the storing up electricity performance of electrode material is improved.
At present, there are many methods with regard to preparing the polypyrrole and polyaniline electrode material of different-shape.Such as
The liquid-liquid interface formed using polyaniline and polypyrrole monomer, is prepared polyaniline and polypyrrole is compound using electrochemical polymerization
Film, but the usual structural disorder of polymeric film that obtains of this preparation method and less with the contact area of electrolyte, are unfavorable for two
Plant making full use of for conducting polymer physical performance.
The content of the invention
Goal of the invention：The present invention provides a kind of while there are three layers of nanotube battle array of novel coaxial of N-shaped doping and p-type doping
Polypyrrole-titanium dioxide-polyaniline or polypyrrole-titanium nitride-polyaniline composite electrode material of array structure and preparation method thereof,
And as ultracapacitor, the electrochemical energy storage application of secondary battery electrode material.
Technical scheme：A kind of polypyrrole-titanium dioxide or the coaxial three layers of nanotube of titanium nitride-polyaniline that the present invention is provided
Array composite material, it is characterised in that：Titanium dioxide or titanium nitride nano pipe array backbone (1) including pipe wall absolute construction,
Titanium dioxide or titanium nitride nano pipe array backbone (1) outside wall surface aggregation deposition polypyrrole nanotube (2) and
The polyaniline nanotube (3) of titanium dioxide or titanium nitride nano pipe array backbone (1) internal face aggregation deposition；The poly- pyrrole
Cough up-titanium dioxide or the coaxial three layers of nanotube array composite material of titanium nitride-polyaniline be that one group of three layer with concentric shafts is received
The array structure that the tight ordered arrangement of mitron is formed, with concentric shafts three layers of described nanometer outer tube layer are polypyrrole nanometer
Pipe, intermediate layer is titanium dioxide or titanium nitride nano pipe, and internal layer is polyaniline nanotube.
Polypyrrole-the titanium dioxide or the coaxial three layers of nanotube array composite material of titanium nitride-polyaniline adulterate p-type
Conductive polymer polypyrrole and N-shaped doping conductive polymer polyanaline are introduced between titanium dioxide or titanium nitride nano cannon born frame
Outside wall surface and internal face, define the composite of p-n junction hetero-junctions polymer features.
Preferably, the pipe thickness of titanium dioxide or titanium nitride nano pipe be 10-20nm, internal diameter be 80-130nm, length
For 860-960nm, distance is 30-68nm between adjacent titanium dioxide or titanium nitride nano pipe；When skeleton is nano titania
During pipe array, the pipe thickness of polypyrrole nanotube is 8-15nm, and the pipe thickness of polyaniline nanotube is 8-11nm；Work as skeleton
For titanium nitride nano pipe array when, the pipe thickness of polypyrrole nanotube is 18-30nm, and the pipe thickness of polyaniline nanotube is
5-15nm。
Present invention also offers a kind of above-mentioned polypyrrole-titanium dioxide or the coaxial three layers of nanotube battle array of titanium nitride-polyaniline
The preparation method of row composite, by chemical polymerization, electrochemical polymerization reaction and light dividing for electrochemical polymerization reaction is helped
Step selectivity synthesis reaction method is prepared from, and comprises the following steps：
(1) preparation of Nano tube array of titanium dioxide：It is anti-in two electrodes chemistry using constant potential anodic oxidation synthetic method
In answering system, using titanium sheet as anode and as working electrode, using platinized platinum as negative electrode and as auxiliary to electrode, to be fluorinated
The mixed aqueous solution of ammonium, phosphoric acid, methanol and ethylene glycol reacts 1- as reaction electrolyte solution under the conditions of constant voltage 20-30V
3h, is obtained the Nano tube array of titanium dioxide of amorphous state；By the Nano tube array of titanium dioxide of amorphous state at 400-500 DEG C
High-temperature calcination 1-3h, is obtained the Nano tube array of titanium dioxide of Anatase；
(2) preparation of titanium nitride nano pipe array：Step (1) is obtained the Nano tube array of titanium dioxide of Anatase pure
Under the conditions of ammonia atmosphere, 900 DEG C of constant temperature nitrogen treatment 1-2h are obtained titanium nitride nano pipe array；
(3) polypyrrole-titanium dioxide of chemical polymerization pretreatment or the polypyrrole-titanium nitride of chemical polymerization pretreatment are compound
The preparation of material：By Nano tube array of titanium dioxide obtained in step (1) or titanium nitride nano pipe array table obtained in step (2)
Face uniform application pyrroles and the carbonic allyl ester solution of ferric chloride, under vacuum condition, 35-45 DEG C of constant temperature processes 6-8min, weight
Multiple 3-5 time, obtain final product chemical polymerization pretreatment polypyrrole-titanium dioxide or chemical polymerization pretreatment polypyrrole-titanium nitride it is multiple
Condensation material；
(4) preparation of polypyrrole-titanium dioxide or polypyrrole-titanium nitride composite material：In three-electrode electro Chemical reactant
In system, with the polypyrrole-titanium dioxide of chemical polymerization pretreatment or the polypyrrole-titanium nitride composite material of chemical polymerization pretreatment
For working electrode, using the Allyl carbonate mixed solution of pyrroles, lithium perchlorate and methanol as reaction electrolyte solution, using rank
Ladder scanning voltammetry electrochemical polymerization reaction is obtained polypyrrole-titanium dioxide or polypyrrole-titanium nitride composite material；
(5) polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization pretreatment or chemical polymerization pretreatment is poly-
The preparation of pyrroles-titanium nitride-polyaniline composite material：By polypyrrole-titanium dioxide or polypyrrole-nitridation obtained in step (4)
Titanium composite material soaks after 5-15min in aniline, the acetonitrile solution of potassium peroxydisulfate, in being inverted in hydrothermal reaction kettle, 55-65 DEG C
Incubation water heating processes 1-2h, and the polypyrrole-titanium dioxide-polyaniline composite material or chemical polymerization of chemical polymerization pretreatment is obtained
Polypyrrole-titanium nitride-the polyaniline composite material of pretreatment；
(6) preparation of coaxial three layers of nanotube array composite material：In three-electrode electro Chemical reaction system, with step
(5) polypyrrole-titanium dioxide-polyaniline composite material or the poly- pyrrole of chemical polymerization pretreatment of chemical polymerization pretreatment obtained in
Cough up-titanium nitride-polyaniline composite material be working electrode, it is water-soluble with aniline, chloro- 2 amino benzoic Acid of 4- and dimethylformamide
Liquid under the irradiation of 1000W xenon lamps, using ladder water price light electrochemical polymerization reaction system is helped as reaction electrolyte solution
Obtain coaxially three layers of nanotube array composite material.
In step (1), in reaction electrolyte solution, the molar concentration of ammonium fluoride is that 0.15-0.30mol/L, phosphoric acid rub
Your concentration is 0.4-0.5mol/L, and it is 35-45% that the volume fraction of methanol is 5-8%, the volume fraction of ethylene glycol；Preferably,
The molar concentration of ammonium fluoride is 0.2mol/L, the molar concentration of phosphoric acid is 0.5mol/L, the volume fraction of methanol is 5%, second two
The volume fraction of alcohol is 40%.
In step (2), pure ammonia atmosphere environment is：Ammonia concentration is 99.0-99.6%, and ammonia flow is 30-50mL/min；
900 DEG C of constant temperature nitrogen treatment programs are：It is warming up to 900 DEG C of constant temperature and processes 1-2h；Heating schedule is：It is 5 from room temperature to 300 DEG C
DEG C/min, and it is 2 DEG C/min from 300 to 700 DEG C, it is 1 DEG C/min from 700 to 900 DEG C.
In step (3), in the carbonic allyl ester solution of pyrroles and ferric chloride, the molar concentration of pyrroles is 0.5-
1.5mol/L, preferred 1.0mol/L, the molar concentration of ferric chloride is 0.025-0.030mol/L, preferred 0.028mol/L.
In step (4), in the Allyl carbonate mixed solution of pyrroles, lithium perchlorate and methanol, the molar concentration of pyrroles is
0.15-0.25mol/L, the molar concentration of lithium perchlorate is 0.05-0.1mol/L, volume fraction 3-5% of methanol；Preferably,
The molar concentration of pyrroles is 0.2mol/L, and the molar concentration of lithium perchlorate is 0.075mol/L, the volume fraction 4% of methanol；Rank
Ladder scans voltammetry condition：Take-off potential is 0.55V, termination current potential be 1.1V, current potential increment be 0.001-0.004V/s, rank
The jump cycle is 0.1-0.4s, and scanning hop count is 3-6.
In step (5), in aniline, the acetonitrile solution of potassium peroxydisulfate, the molar concentration of aniline is 0.05-0.15mol/L, mistake
The molar concentration of potassium sulfate is 0.04-0.06mol/L, it is preferable that the molar concentration of aniline is 0.10mol/L, potassium peroxydisulfate
Molar concentration is 0.05mol/L.
In step (6), in the chloro- amino benzoic Acid of aniline, 4- and dimethylformamide in water, the molar concentration of aniline is
The molar concentration of chloro- 2 amino benzoic Acid of 0.05-0.2mol/L, 4- is 0.3-0.5mol/L, the volume fraction of dimethylformamide
For 5-10%；Ladder water price condition is：Take-off potential is -0.2V, and termination current potential is 1.0V, and current potential increment is 0.001-
0.004V/s, the step cycle is 0.2-0.8s, and scanning hop count is 5-10.A kind of polypyrrole described in any one of claim 1-2-
Application in titanium dioxide or the coaxial three layers of nanotube array composite material electrochemical energy storage field of titanium nitride-polyaniline.
Present invention also offers polypyrrole-titanium dioxide or the coaxial three layers of nano-tube array composite wood of polypyrrole-titanium nitride
Application of the material in electrochemical energy storage field, specially：Using above-mentioned coaxial three layers of nanotube array composite material as positive negative electricity
In ultracapacitor, working electrolyte is the sulphuric acid (H of liquid phase to pole materials application2SO4), phosphoric acid (H3PO4), perchloric acid
(HClO4) aqueous solution or solid-state phase lithium perchlorate-phosphoric acid-polyvinyl alcohol (LiClO4-H3PO4- PVA) gel.
Beneficial effect：Coaxial three layers of nanotube array composite material that the present invention is provided is with titanium dioxide or titanium nitride nano
Pipe array is obtained for skeleton, and titanium dioxide or titanium nitride nano pipe are not only that deposited polymer provides orderly skeleton, and
Its hollow structure and uniform tube pitch can absorb the volume contraction and expansion caused during conducting polymer discharge and recharge, so as to
Strengthen the cycle life of electrode material；Lacunose hollow tubular structure causes polyaniline and polypyrrole to fill with dopant electrolyte
Tap is touched, and is conducive to electrolyte ion to spread and electric charge transfer, and composite materials are simultaneously comprising p-type doping characteristic polypyrrole and n
Type doping characteristic polyaniline, makes full use of anions and canons in solution, so as to obtain high specific capacitance, good cycling stability it is super
Capacitor electrode material.
Specifically, it is of the invention relative to prior art, with advantage following prominent：
(1) coaxial three layers of nanotube array composite material that the present invention is provided is respectively by polypyrrole nanotube, titanium dioxide
Or titanium nitride nano pipe and polyaniline nanotube successively ordered fabrication is formed, have concurrently p-type doping conducting polymer and N-shaped doping lead
Electric polymer, during cycle charge-discharge, can be while mixing with electrolytic anion, cation generation p-type doping and N-shaped is matched
Miscellaneous reaction, has high specific capacitance value and good circulation stability concurrently.
(2) preparation method of coaxial three layers of nanotube array composite material that the present invention is provided, between the pipe using nanotube
The selective polymerisation of regulation and control is realized away from the polymerization activity diversity with pipe interface stress diversity, pyrroles and aniline monomer
Reactive deposition.Polypyrrole forms poly- using the chemical polymerization nucleation pretreatment under vacuum condition and electrochemical polymerization reactive deposition
Aniline nano pipe, polyaniline helps electrochemical polymerization reactive deposition using the chemical polymerization nucleation pretreatment under hydrothermal condition and light
Polypyrrole nanotube is formed, polypyrrole and polyaniline both polymeric oxidizers ground substeps, subregion has been regulated and controled well and has been sunk
Product is on titanium dioxide or titanium nitride skeleton.Electric polymerization reaction synthetic method employs ladder water price, compared to general
Using the method such as cyclic voltammetry, galvanostatic method, potentiostatic method, ladder water price can preferably control polyreaction,
Make polypyrrole preferentially in the pipe outer wall face of titanium dioxide or titanium nitride nano pipe deposition.
(3) coaxial three layers of nanotube array composite material is applied to into super capacitor function electrode, in titanium dioxide or
Simultaneously N-shaped conductive polymer polypyrrole and p-type electric-conducting polymer polyanaline are introduced in titanium nitride nano cannon born frame, in electrochemistry
During cycle charge-discharge, two kinds of conducting polymers simultaneously with electrolyte solution in anion and cation be doped instead
Should, charge transfer rate is improve, increased the electrochemical energy storage performance of electrode material.Coaxial three layers of nano-tube array structure is not only
Be conducive to electrode active material to be fully contacted with electrolyte, reduce charge transfer resistance, and hollow structure can also absorb
The volume contraction caused during macromolecular material discharge and recharge and expansion, so as to strengthen the cycle life of electrode material.Described is coaxial
The specific capacitance of the polypyrrole-titanium dioxide-polyaniline composite material of three layers of nano-tube array structure can reach 450-600F/g,
Cycle life can be reached more than 1000 times (capacitance conservation rate is 75-85%)；Described coaxial three layers of nano-tube array knot
The specific capacitance of the polypyrrole-titanium nitride-polyaniline composite material of structure can reach 1800-2000F/g, and cycle life can be reached
More than 1000 times (capacitance conservation rate is 81-91%).As can be seen here, coaxial three layers of nano-tube array that the present invention is provided is combined
Material has higher specific capacity value and preferable cyclical stability, is the active electrode material of high-efficiency energy-storage type, with very
Wide application prospect.
Description of the drawings
Fig. 1 is the structural representation of the coaxial three layers of nanotube array composite material of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of titanium dioxide or titanium nitride nano pipe, wherein (a) is front elevation, (b) it is side view.
Fig. 3 is the scanning electron microscope (SEM) photograph of polypyrrole-composite titania material, wherein (a) front elevation, (b) is side view.
Fig. 4 is the scanning electron microscope (SEM) photograph of polypyrrole-titanium dioxide-polyaniline composite material, wherein (a) is front elevation, (b) is
Side view.
Fig. 5 is the scanning electron microscope (SEM) photograph of polypyrrole-titanium nitride composite material, wherein (a) is front elevation, (b) it is side view.
Fig. 6 is the scanning electron microscope (SEM) photograph of polypyrrole-titanium nitride-polyaniline composite material, wherein (a) is front elevation, (b) it is side
Face figure.
Fig. 7 be (a) titania nanotube, (b) polypyrrole-composite titania material, (c) polyaniline-titanium dioxide
The Raman spectrogram of composite and (d) polypyrrole-titanium dioxide-polyaniline composite material.
Fig. 8 be (a) titanium nitride nano pipe, (b) polypyrrole-titanium nitride composite material, (c) polyaniline-titanium nitride composite wood
Material, (d) Raman spectrogram of polypyrrole-titanium nitride-polyaniline composite material.
Fig. 9 is that (a) polypyrrole-composite titania material and (b) polypyrrole-titanium dioxide-polyaniline composite material exist
0.5mol/L H2SO4Cyclic voltammetry curve in solution, under the conditions of 20mV/s sweep speeds.
Figure 10 is that (a) polypyrrole-composite titania material and (b) polypyrrole-titanium dioxide-polyaniline composite material exist
0.5mol/L H2SO4Constant current charge-discharge curve in solution, under 0.5A/g electric current densities.
Figure 11 is that (a) polypyrrole-titanium dioxide-polyaniline composite material and (b) polypyrrole-titanium nitride-polyaniline are combined
Material is in 0.5mol/L H2SO4Cyclic voltammetry curve in solution, under the conditions of 100mV/s sweep speeds.
Figure 12 is that (a) polypyrrole-titanium dioxide-polyaniline composite material and (b) polypyrrole-titanium nitride-polyaniline are combined
Material is in 0.5mol/L H2SO4Constant current charge-discharge curve in solution, under 1.0A/g electric current densities.
Specific embodiment
There can be preferably elaboration to the present invention by the following examples, but these embodiments are it is not intended that to this
The restriction of bright scope.
Embodiment 1
(1) titanium dioxide and titanium nitride nano pipe array backbone material are prepared：By titanium sheet successively ethanol, acetone, go from
Be cleaned by ultrasonic 30min in sub- water, after taking-up volume ratio be 1:4:Polishing in 5 fluohydric acid gas/nitric acid/water solution；Two
In electrode electro Chemical reaction system, titanium sheet as anode, platinized platinum as negative electrode, with the ammonium fluoride of 0.2mol/L, 0.5mol/L
The aqueous solution of phosphoric acid, the methanol of volume fraction 5% and the ethylene glycol of volume fraction 40% is reaction electrolyte solution, using anodic oxidation
Method, under the conditions of constant voltage 30V, 25 DEG C of isothermal reaction 2h dry naturally after then deionized water is fully rinsed, and pipe is obtained
Wall independence, the unlimited Nano tube array of titanium dioxide of the mouth of pipe.High-temperature calcination processes Nano tube array of titanium dioxide, and design temperature is
450 DEG C, the response time is 2h, and the Nano tube array of titanium dioxide of Anatase is obtained；High-temperature ammonolysis process nano titania
Pipe array, sets ammonia concentration as 99.6%, and ammonia flow is 50mL/min, and reaction temperature is 900 DEG C, and the response time is 1h,
Heating rate is：From room temperature to 300 DEG C be 5 DEG C/min, from 300 to 700 DEG C be 2 DEG C/min, from 700 to 900 DEG C be 1 DEG C/
Min, is obtained titanium nitride nano pipe array.The scanning electron microscope (SEM) photograph of Nano tube array of titanium dioxide and sweeping for titanium nitride nano pipe array
Retouch electron microscope basically identical, its front elevation and side view show, pipe thickness is 10-20nm, internal diameter is 80-130nm, length is
860-960nm, distance is 30-68nm between adjacent titanium dioxide or titanium nitride nano pipe, and nanotube ordered arrangement, the mouth of pipe is opened
Open, pattern is uniform, sees Figure of description 2.
(2) polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure is prepared：As bone
The titania nanotube surface uniform application 1.0mol/L pyrroles of frame and the Allyl carbonate of 0.028mol/L ferric chlorides are molten
Liquid, under 40 DEG C of constant temperature and vacuum condition 6min is processed, and said process is repeated 5 times, and the poly- pyrrole of chemical polymerization pretreatment is obtained
Cough up-composite titania material；In three-electrode electro Chemical reaction system, with the polypyrrole-two of chemical polymerization pretreatment
Titanium oxide composite material is working electrode, with 0.2mol/L pyrroles, 0.1mol/L lithium perchlorates, the methanol of volume fraction 4% carbon
Acid propylene ester is that solvent constitutes reaction electrolyte solution, and electrochemical polymerization reaction adopts ladder water price, arranges starting electricity
Position is 0.55V, and termination current potential is 1.1V, and current potential increment is 0.001V/s, and the step cycle is 0.1s, and scanning hop count is 6, Bi Kadan
Body is obtained coaxial two layers of nanometer optionally in titania nanotube outside wall surface homogeneous polymerization formation of deposits polypyrrole nanotube
Polypyrrole-the composite titania material of pipe array structure.Polypyrrole-the titanium dioxide of coaxial two layers of nano-tube array structure
Titanium composite material soaks to be taken out after 10min in 0.1mol/L aniline, the acetonitrile solution of 0.05mol/L potassium peroxydisulfates and is inverted in water
In thermal response kettle, 1h is processed under 60 DEG C of constant temperature and hydrothermal condition, the polypyrrole-dioxy of hydrothermal chemistry polyreaction pretreatment is obtained
Change titanium-polyaniline composite material；In three-electrode electro Chemical reaction system, with the polypyrrole-two of chemical polymerization pretreatment
Titanium oxide-polyaniline composite material is working electrode, with 0.2mol/L aniline, chloro- 2 amino benzoic Acid of 0.4mol/L4-, volume
The dimethylformamide of fraction 8% constitutes reaction electrolyte solution, and under the irradiation of 1000W xenon lamps, light helps electrochemical polymerization to react
Using ladder water price is adopted, setting take-off potential is -0.2V, and termination current potential is 1.0V, and current potential increment is 0.001V/s,
The step cycle is 0.2s, and scanning hop count is 8, and aniline monomer optionally reacts in titania nanotube internal face homogeneous polymerization
Formation of deposits polyaniline nanotube, is obtained the polypyrrole-titanium dioxide-polyaniline composite wood of coaxial three layers of nano-tube array structure
Material.
The scanning electron microscope front elevation of the polypyrrole-composite titania material of coaxial two layers of nano-tube array structure shows,
Polypyrrole is selectively deposited in titania nanotube outside wall surface, and the pipe thickness of polypyrrole nanotube is 8-15nm, is seen
Bright book accompanying drawing 3.
The scanning electron microscope front of the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure
Figure and side view show that polyaniline selective deposition is in titania nanotube internal face, the pipe thickness of polyaniline nanotube
For 8-11nm, additionally, the strata Aniline Films of titania nanotube mouth of pipe formation of deposits one, its thickness is 20-45nm, sees description
Accompanying drawing 4.
The micro structure of the polypyrrole-titanium dioxide-polyaniline composite material, structural representation are understood by Figure of description 4
See Fig. 1, it is heavy that the Nano tube array of titanium dioxide with pipe wall absolute construction is polymerized as skeleton, in titania nanotube outside wall surface
Product forms polypyrrole nanotube, and aggregation deposition forms polyaniline nanotube on titania nanotube internal face, by two
Titania nanotube array 1, the polypyrrole nanotube 2 formed in the outside wall surface of titania nanotube 1, and nano titania
The polyaniline nanotube 3 formed on the internal face of pipe 1, together form the polypyrrole-dioxy of coaxial three layers of nano-tube array structure
Change titanium-polyaniline composite material.
(3) polypyrrole-titanium nitride-polyaniline composite material of coaxial three layers of nano-tube array structure is prepared：As skeleton
Titanium nitride nano pipe array surface uniform application 1.0mol/L pyrroles and 0.028mol/L ferric chlorides Allyl carbonate it is molten
Liquid, under 40 DEG C of constant temperature and vacuum condition 6min is processed, and said process is repeated 5 times, and the poly- pyrrole of chemical polymerization pretreatment is obtained
Cough up-titanium nitride composite material；It is multiple with the polypyrrole-titanium nitride of chemical polymerization pretreatment in three-electrode electro Chemical reaction system
Condensation material is working electrode, with 0.2mol/L pyrroles, 0.05mol/L lithium perchlorates, the methanol of volume fraction 4% Allyl carbonate
Reaction electrolyte solution is constituted for solvent, electrochemical polymerization reaction adopts ladder water price, take-off potential is set and is
0.55V, termination current potential is 1.1V, and current potential increment is 0.001V/s, and the step cycle is 0.1s, and scanning hop count is 4, pyrrole monomer choosing
Selecting property in titanium nitride nano pipe outer wall face homogeneous polymerization formation of deposits polypyrrole nanotube, be obtained coaxial two layers of nano-tube array
Polypyrrole-the titanium nitride composite material of structure.Described polypyrrole/titanium nitride composite material 0.1mol/L aniline,
Soak in the acetonitrile solution of 0.05mol/L potassium peroxydisulfates and take out and be inverted in hydrothermal reaction kettle after 10min, 60 DEG C of constant temperature and hydro-thermal
Under the conditions of process 1h, the polypyrrole-titanium nitride-polyaniline composite material of chemical polymerization pretreatment is obtained；In three electrodes electricity
In chemical reaction system, the polypyrrole-titanium nitride-polyaniline composite material with chemical polymerization pretreatment as working electrode,
Reaction electricity is constituted with the dimethylformamide of 0.1mol/L aniline, chloro- 2 amino benzoic Acid of 0.4mol/L4-, volume fraction 10%
Electrolyte solution, under the irradiation of 1000W xenon lamps, light helps electrochemical polymerization reaction to adopt ladder water price, arranges starting
Current potential is -0.2V, and termination current potential is 1.0V, and current potential increment is 0.004V/s, and the step cycle is 0.8s, and scanning hop count is 6, aniline
Monomer selectivity ground is obtained coaxial three layers of nanometer in titanium nitride nano inside pipe wall face homogeneous polymerization formation of deposits polyaniline nanotube
Polypyrrole-titanium nitride-the polyaniline composite material of pipe array structure.
The scanning electron microscope front elevation of the polypyrrole/titanium nitride composite material of coaxial two layers of nano-tube array structure shows, gathers
Pyrroles is selectively deposited in titanium nitride nano pipe outer wall face, and the pipe thickness of polypyrrole nanotube is 18-30nm, sees description
Accompanying drawing 5.
The scanning electron microscope front elevation of the polypyrrole/titanium nitride/polyaniline composite material of coaxial three layers of nano-tube array structure
Show with side view, in titanium nitride nano inside pipe wall face, the pipe thickness of polyaniline nanotube is 5- to polyaniline selective deposition
15nm, is shown in Figure of description 6.
The structure of the polypyrrole-titanium nitride-polyaniline composite material is understood by Figure of description 4, structural representation is shown in figure
1, as skeleton, aggregation deposition forms poly- to the titanium nitride nano pipe array with pipe wall absolute construction on titanium nitride nano pipe outer wall face
Pyrroles's nanotube, and aggregation deposition forms polyaniline nanotube on titanium nitride nano inside pipe wall face, by titanium nitride nano pipe
Array 1, the polypyrrole nanotube 2 formed in the outside wall surface of titanium nitride nano pipe 1, and formed on the internal face of titanium nitride nano pipe 1
Polyaniline nanotube 3, together form the polypyrrole-titanium nitride-polyaniline composite wood of coaxial three layers of nano-tube array structure
Material.
Structural analyses：
Contrast Nano tube array of titanium dioxide, the polypyrrole-titanium dioxide composite wood of coaxial two layers of nano-tube array structure
Material, the polyaniline-composite titania material of coaxial two layers of nano-tube array structure, coaxial three layers of nano-tube array structure it is poly-
The Raman spectrum test result of pyrroles-titanium dioxide-polyaniline composite material shows, coaxial three layers of nano-tube array structure it is poly-
Pyrroles-titanium dioxide-polyaniline composite material occurs in that the characteristic peak of titanium dioxide, polypyrrole, polyaniline simultaneously, in 150cm-1,607cm-1,1180cm-1,1347cm-1,1493cm-1The obvious characteristic peak of appearance corresponds respectively to O-Ti-O and becomes angular oscillation, benzene
The stretching vibration of the stretching vibration of ring, C-H bending vibrations, C-N stretching vibration peaks, quinone and semiquinone, therefore, polypyrrole, polyaniline
Simultaneously Nano tube array of titanium dioxide skeleton is deposited on, sees Figure of description 7.
It is contrast titanium nitride nano pipe array, the polypyrrole-titanium nitride composite material of coaxial two layers of nano-tube array structure, same
Polypyrrole-the nitrogen of the polyaniline-titanium nitride composite material of two layers of nano-tube array structure of axle, coaxial three layers of nano-tube array structure
Change titanium/polyaniline composite material Raman spectrum test result show, the polypyrrole-nitridation of coaxial three layers of nano-tube array structure
Titanium-polyaniline composite material occurs in that the characteristic peak of titanium nitride, polypyrrole, polyaniline simultaneously, in 210cm-1And 570cm-1Occur
Wide characteristic peak correspond respectively to titanium nitride crystal TA and TO Raman vibration mould, in 936cm-1, 1060cm-1Corresponding to C-H rings
Deformation vibration, 1380cm-1,1509cm-1,1599cm-1The obvious characteristic peak of appearance corresponds respectively to C-N stretching vibrations, C=N and stretches
Contracting vibration, C=C stretching vibration peaks, it was demonstrated that polypyrrole, polyaniline are deposited on titanium nitride nano pipe array backbone simultaneously, see
Figure of description 8.
Test chemical property：
(1) electrochemical capacitor of the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure
Performance.
Electrochemical property test is carried out in three-electrode system using CHI760 electrochemical workstations, with coaxial three layers of nanometer
Polypyrrole-titanium dioxide-the polyaniline composite material of pipe array structure is working electrode, and platinized platinum is to electrode, saturation calomel electricity
Extremely reference electrode, 0.5mol/L H2SO4Solution is working electrolyte, and during electrochemistry cyclic voltammetry, sweep speed is
20mV/s, the symmetry redox peaks that cyclic voltammetry curve occur embody it and go out preferable electrochemical reaction reversibility feature, see
Figure of description 9.
With CHI760 electrochemical workstation electro-chemical test cycle charge discharge electrical properties, constant current density is 0.5A/g, is passed through
The specific capacitance for being calculated polypyrrole-composite titania material and polypyrrole-titanium dioxide-polyaniline composite material is respectively
300F/g and 496F/g, specific capacitance improves about 65%, sees Figure of description 10.
(2) electrochemical capacitor of the polypyrrole-titanium nitride-polyaniline composite material of coaxial three layers of nano-tube array structure
Energy.
Electrochemical property test is carried out in three-electrode system using CHI760 electrochemical workstations, with coaxial three layers of nanometer
Polypyrrole-titanium nitride-the polyaniline composite material of pipe array structure is working electrode, and platinized platinum is to electrode, saturated calomel electrode
For reference electrode, 0.5mol/L H2SO4Solution is working electrolyte, and during electrochemistry cyclic voltammetry, sweep speed is
100mV/s, the symmetry redox peaks that cyclic voltammetry curve occur embody it and go out preferable electrochemical reaction reversibility feature, see
Figure of description 11.
With CHI760 electrochemical workstation electro-chemical test cycle charge discharge electrical properties, constant current density is 1.0A/g, is passed through
It is calculated the specific capacitance of polypyrrole-titanium dioxide-polyaniline composite material and polypyrrole/titanium nitride/polyaniline composite material
Respectively 293.4F/g and 1847F/g, specific capacitance improves about 5 times, sees Figure of description 12.
Embodiment 2
The preparation method of polypyrrole-titanium dioxide-polyaniline composite material, by chemical polymerization, electrochemical polymerization
Reaction and light help the substep selectivity synthesis reaction method that electrochemical polymerization is reacted to be prepared from, and comprise the following steps：
(1) preparation of Nano tube array of titanium dioxide：Titanium sheet is cleaned by ultrasonic successively in ethanol, acetone, deionized water
30min, after taking-up volume ratio be 1:4:Polishing in 5 fluohydric acid gas/nitric acid/water solution；Using constant potential anodic oxidation
Synthetic method, in two electrode chemical reaction systems, as anode and as working electrode, platinized platinum is used as negative electrode simultaneously conduct for titanium sheet
Aid in electrode, with the ammonium fluoride of 0.25mol/L, the phosphoric acid of 0.4mol/L, the methanol of volume fraction 5% and volume fraction as 40%
The aqueous solution of ethylene glycol is reaction electrolyte solution, and under the conditions of constant voltage 20V 2h is reacted, and the titanium dioxide of amorphous state is obtained
Nano-tube array；Secondly, high-temperature calcination processes the Nano tube array of titanium dioxide of amorphous state, and design temperature is 450 DEG C, reaction
Time is 2h, and the Nano tube array of titanium dioxide of Anatase is obtained；
(2) preparation of the polypyrrole-composite titania material of chemical polymerization pretreatment：Nano tube array of titanium dioxide table
Face uniform application 1.0mol/L pyrroles and the carbonic allyl ester solution of 0.028mol/L ferric chlorides, 40 DEG C of constant temperature and vacuum condition
Lower process 7min, said process is repeated 4 times, and the polypyrrole-composite titania material of chemical polymerization pretreatment is obtained.
(3) preparation of the polypyrrole-composite titania material of coaxial two layers of nano-tube array structure：In three electrode electrochemicals
Learn reaction system in, the polypyrrole-titanium dioxide with chemical polymerization pretreatment as working electrode, with 0.2mol/L pyrroles,
0.075mol/L lithium perchlorates, the Allyl carbonate of the methanol of volume fraction 4% are that solvent constitutes reaction electrolyte solution, electrochemistry
Polyreaction adopts ladder water price, and setting take-off potential is 0.55V, and termination current potential is 1.1V, and current potential increment is
0.002V/s, the step cycle is 0.2s, and scanning hop count is 4, and pyrrole monomer is optionally equal in titania nanotube outside wall surface
Even aggregation deposition forms polypyrrole nanotube, and the polypyrrole-titanium dioxide composite wood of coaxial two layers of nano-tube array structure is obtained
Material.
(4) preparation of the polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization pretreatment：Obtained coaxial two
Layer nano-tube array structure polypyrrole-composite titania material composite is in 0.1mol/L aniline, 0.05mol/L persulfuric acid
Soak to be taken out after 10min in the acetonitrile solution of potassium and be inverted in hydrothermal reaction kettle, under 60 DEG C of constant temperature and hydrothermal condition 1-2h is processed,
Polypyrrole-titanium dioxide-the polyaniline composite material of prepared chemical polymerization pretreatment.
(5) preparation of the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure：Three
In electrode electro Chemical reaction system, with the polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization pretreatment as work electricity
Pole, with the dimethylformamide of 0.1mol/L aniline, chloro- 2 amino benzoic Acid of 0.4mol/L4-, volume fraction 7% reaction is constituted
Electrolyte solution, under the irradiation of 1000W xenon lamps, light helps electrochemical polymerization reaction to adopt ladder water price, arranges starting electricity
Position is -0.2V, and termination current potential is 1.0V, and current potential increment is 0.002V/s, and the step cycle is 0.5s, and scanning hop count is 7, aniline list
Body is obtained coaxial three layers of nanometer optionally in titania nanotube internal face homogeneous polymerization formation of deposits polyaniline nanotube
Polypyrrole-titanium dioxide-the polyaniline composite material of pipe array structure.
Embodiment 3
The preparation method of polypyrrole-titanium dioxide-polyaniline composite material, by chemical polymerization, electrochemical polymerization
Reaction and light help the substep selectivity synthesis reaction method that electrochemical polymerization is reacted to be prepared from, and comprise the following steps：
(1) preparation of Nano tube array of titanium dioxide：Titanium sheet is cleaned by ultrasonic successively in ethanol, acetone, deionized water
30min, after taking-up volume ratio be 1:4:Polishing in 5 fluohydric acid gas/nitric acid/water solution；Using constant potential anodic oxidation
Synthetic method, in two electrode chemical reaction systems, as anode and as working electrode, platinized platinum is used as negative electrode simultaneously conduct for titanium sheet
Aid in electrode, with the ammonium fluoride of 0.15mol/L, the phosphoric acid of 0.5mol/L, the methanol of volume fraction 6% and volume fraction as 40%
The aqueous solution of ethylene glycol is reaction electrolyte solution, and under the conditions of constant voltage 30V 1h is reacted, and the titanium dioxide of amorphous state is obtained
Nano-tube array；Secondly, high-temperature calcination processes the Nano tube array of titanium dioxide of amorphous state, and design temperature is 400 DEG C, reaction
Time is 3h, and the Nano tube array of titanium dioxide of Anatase is obtained；
(2) preparation of the polypyrrole-composite titania material of chemical polymerization pretreatment：Nano tube array of titanium dioxide table
Face uniform application 0.5mol/L pyrroles and the carbonic allyl ester solution of 0.025mol/L ferric chlorides, 35 DEG C of constant temperature and vacuum condition
Lower process 8min, said process is repeated 3 times, and the polypyrrole-composite titania material of chemical polymerization pretreatment is obtained.
(3) preparation of the polypyrrole-composite titania material of coaxial two layers of nano-tube array structure：In three electrode electrochemicals
Learn reaction system in, the polypyrrole-titanium dioxide with chemical polymerization pretreatment as working electrode, with 0.15mol/L pyrroles,
0.1mol/L lithium perchlorates, the Allyl carbonate of the methanol of volume fraction 3% are that solvent constitutes reaction electrolyte solution, and electrochemistry is gathered
Close reaction and adopt ladder water price, setting take-off potential is 0.55V, and termination current potential is 1.1V, and current potential increment is 0.004V/
S, the step cycle is 0.1s, and scanning hop count is 3, and pyrrole monomer is optionally heavy in titania nanotube outside wall surface homogeneous polymerization
Product forms polypyrrole nanotube, and the polypyrrole-composite titania material of coaxial two layers of nano-tube array structure is obtained.
(4) preparation of the polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization pretreatment：Obtained coaxial two
Layer nano-tube array structure polypyrrole-composite titania material composite is in 0.05mol/L aniline, 0.04mol/L over cures
Soak to be taken out after 15min in the acetonitrile solution of sour potassium and be inverted in hydrothermal reaction kettle, under 55 DEG C of constant temperature and hydrothermal condition 2h is processed,
Polypyrrole-titanium dioxide-the polyaniline composite material of prepared chemical polymerization pretreatment.
(5) preparation of the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure：Three
In electrode electro Chemical reaction system, with the polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization pretreatment as work electricity
Pole, with the dimethylformamide of 0.05mol/L aniline, chloro- 2 amino benzoic Acid of 0.5mol/L4-, volume fraction 5% reaction is constituted
Electrolyte solution, under the irradiation of 1000W xenon lamps, light helps electrochemical polymerization reaction to adopt ladder water price, arranges starting electricity
Position is -0.2V, and termination current potential is 1.0V, and current potential increment is 0.004V/s, and the step cycle is 0.8s, and scanning hop count is 5, aniline list
Body is obtained coaxial three layers of nanometer optionally in titania nanotube internal face homogeneous polymerization formation of deposits polyaniline nanotube
Polypyrrole-titanium dioxide-the polyaniline composite material of pipe array structure.
Embodiment 4
The preparation method of polypyrrole-titanium dioxide-polyaniline composite material, by chemical polymerization, electrochemical polymerization
Reaction and light help the substep selectivity synthesis reaction method that electrochemical polymerization is reacted to be prepared from, and comprise the following steps：
(1) preparation of Nano tube array of titanium dioxide：Titanium sheet is cleaned by ultrasonic successively in ethanol, acetone, deionized water
30min, after taking-up volume ratio be 1:4:Polishing in 5 fluohydric acid gas/nitric acid/water solution；Using constant potential anodic oxidation
Synthetic method, in two electrode chemical reaction systems, as anode and as working electrode, platinized platinum is used as negative electrode simultaneously conduct for titanium sheet
Aid in electrode, with the ammonium fluoride of 0.3mol/L, the phosphoric acid of 0.4mol/L, the methanol of volume fraction 8% and volume fraction as 35%
The aqueous solution of ethylene glycol is reaction electrolyte solution, and under the conditions of constant voltage 20V 3h is reacted, and the titanium dioxide of amorphous state is obtained
Nano-tube array；Secondly, high-temperature calcination processes the Nano tube array of titanium dioxide of amorphous state, and design temperature is 500 DEG C, reaction
Time is 1h, and the Nano tube array of titanium dioxide of Anatase is obtained；
(2) preparation of the polypyrrole-composite titania material of chemical polymerization pretreatment：Nano tube array of titanium dioxide table
Face uniform application 1.5mol/L pyrroles and the carbonic allyl ester solution of 0.030mol/L ferric chlorides, 45 DEG C of constant temperature and vacuum condition
Lower process 6min, said process is repeated 5 times, and the polypyrrole-composite titania material of chemical polymerization pretreatment is obtained.
(3) preparation of the polypyrrole-composite titania material of coaxial two layers of nano-tube array structure：In three electrode electrochemicals
Learn reaction system in, the polypyrrole-titanium dioxide with chemical polymerization pretreatment as working electrode, with 0.25mol/L pyrroles,
0.05mol/L lithium perchlorates, the Allyl carbonate of the methanol of volume fraction 5% are that solvent constitutes reaction electrolyte solution, electrochemistry
Polyreaction adopts ladder water price, and setting take-off potential is 0.55V, and termination current potential is 1.1V, and current potential increment is
0.001V/s, the step cycle is 0.4s, and scanning hop count is 6, and pyrrole monomer is optionally equal in titania nanotube outside wall surface
Even aggregation deposition forms polypyrrole nanotube, and the polypyrrole-titanium dioxide composite wood of coaxial two layers of nano-tube array structure is obtained
Material.
(4) preparation of the polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization pretreatment：Obtained coaxial two
Layer nano-tube array structure polypyrrole-composite titania material composite is in 0.15mol/L aniline, 0.06mol/L over cures
Soak to be taken out after 5min in the acetonitrile solution of sour potassium and be inverted in hydrothermal reaction kettle, under 65 DEG C of constant temperature and hydrothermal condition 1h is processed,
Polypyrrole-titanium dioxide-the polyaniline composite material of prepared chemical polymerization pretreatment.
(5) preparation of the polypyrrole-titanium dioxide-polyaniline composite material of coaxial three layers of nano-tube array structure：Three
In electrode electro Chemical reaction system, with the polypyrrole-titanium dioxide-polyaniline composite material of chemical polymerization pretreatment as work electricity
Pole, with the dimethylformamide of 0.2mol/L aniline, chloro- 2 amino benzoic Acid of 0.3mol/L4-, volume fraction 10% reaction is constituted
Electrolyte solution, under the irradiation of 1000W xenon lamps, light helps electrochemical polymerization reaction to adopt ladder water price, arranges starting electricity
Position is -0.2V, and termination current potential is 1.0V, and current potential increment is 0.001V/s, and the step cycle is 0.2s, and scanning hop count is 10, aniline
Monomer selectivity ground is obtained coaxial three layers and receives in titania nanotube internal face homogeneous polymerization formation of deposits polyaniline nanotube
Polypyrrole-titanium dioxide-the polyaniline composite material of mitron array structure.
Embodiment 5
The preparation method of polypyrrole-titanium nitride-polyaniline composite material, it is anti-by chemical polymerization, electrochemical polymerization
With light the substep selectivity synthesis reaction method that electrochemical polymerization is reacted should be helped to be prepared from, be comprised the following steps：
(1) preparation of titanium nitride nano pipe array：Titanium sheet is cleaned by ultrasonic successively in ethanol, acetone, deionized water
30min, after taking-up volume ratio be 1:4:Polishing in 5 fluohydric acid gas/nitric acid/water solution；Using constant potential anodic oxidation
Synthetic method, in two electrode chemical reaction systems, as anode and as working electrode, platinized platinum is used as negative electrode simultaneously conduct for titanium sheet
Aid in electrode, with the ammonium fluoride of 0.2mol/L, the phosphoric acid of 0.4mol/L, the methanol of volume fraction 5% and volume fraction as 40%
The aqueous solution of ethylene glycol is reaction electrolyte solution, and under the conditions of constant voltage 30V 2h is reacted, and the titanium dioxide of amorphous state is obtained
Nano-tube array；Secondly, high-temperature calcination processes the Nano tube array of titanium dioxide of amorphous state, and design temperature is 450 DEG C, reaction
Time is 2h, and the Nano tube array of titanium dioxide of Anatase is obtained；Then, high-temperature ammonolysis process the titanium dioxide of Anatase
Nano-tube array, sets ammonia concentration as 99.6%, and ammonia flow is 40mL/min, is warming up to 900 DEG C of reaction 1.5h, and heat up speed
Rate is：It is 5 DEG C/min from room temperature to 300 DEG C, is 2 DEG C/min from 300 to 700 DEG C, be 1 DEG C/min from 700 to 900 DEG C, is obtained
Titanium nitride nano pipe array.
(2) preparation of the polypyrrole-titanium nitride composite material of chemical polymerization pretreatment：Titanium nitride nano pipe array surface is equal
The even carbonic allyl ester solution for smearing 1.0mol/L pyrroles and 0.028mol/L ferric chlorides, locates under 40 DEG C of constant temperature and vacuum condition
Reason 7min, said process is repeated 4 times, and the polypyrrole-titanium nitride composite material of chemical polymerization pretreatment is obtained.
(3) preparation of the polypyrrole-titanium nitride composite material of coaxial two layers of nano-tube array structure：In three-electrode electro Chemical
In reaction system, the polypyrrole-titanium nitride composite material with chemical polymerization pretreatment as working electrode, with 0.2mol/L pyrroles,
0.075mol/L lithium perchlorates, the Allyl carbonate of the methanol of volume fraction 4% are that solvent constitutes reaction electrolyte solution, electrochemistry
Polyreaction adopts ladder water price, and setting take-off potential is 0.55V, and termination current potential is 1.1V, and current potential increment is
0.002V/s, the step cycle is 0.2s, and scanning hop count is 5, and pyrrole monomer is optionally uniform in titanium nitride nano pipe outer wall face
Aggregation deposition forms polypyrrole nanotube, and the polypyrrole-titanium nitride composite material of coaxial two layers of nano-tube array structure is obtained.
(4) preparation of the polypyrrole-titanium nitride-polyaniline composite material of chemical polymerization pretreatment：Obtained coaxial two layers
Nano-tube array structure polypyrrole-titanium nitride composite material is in 0.1mol/L aniline, the acetonitrile solution of 0.05mol/L potassium peroxydisulfates
Take out after middle immersion 10min and be inverted in hydrothermal reaction kettle, under 60 DEG C of constant temperature and hydrothermal condition 1.5h is processed, chemical polymerization is obtained
Polypyrrole-titanium nitride-the polyaniline composite material of pretreatment.
(5) preparation of the polypyrrole-titanium nitride-polyaniline composite material of coaxial three layers of nano-tube array structure：It is electric three
In the electrochemical reaction system of pole, the polypyrrole-titanium nitride-polyaniline composite material with chemical polymerization pretreatment as working electrode,
Reaction electricity is constituted with the dimethylformamide of 0.01mol/L aniline, chloro- 2 amino benzoic Acid of 0.4mol/L4-, volume fraction 7%
Electrolyte solution, under the irradiation of 1000W xenon lamps, light helps electrochemical polymerization reaction to adopt ladder water price, arranges take-off potential
For -0.2V, termination current potential is 1.0V, and current potential increment is 0.002V/s, and the step cycle is 0.6s, and scanning hop count is 7, aniline monomer
Optionally in titanium nitride nano inside pipe wall face homogeneous polymerization formation of deposits polyaniline nanotube, coaxial three layers of nanotube battle array is obtained
Polypyrrole-titanium nitride-the polyaniline composite material of array structure.
Embodiment 6
It is substantially the same manner as Example 5, the difference is that only:High-temperature ammonolysis process Nano tube array of titanium dioxide, setting
Ammonia concentration is 99.0%, and ammonia flow is 30mL/min, is warming up to 900 DEG C of reaction 2h.
Embodiment 7
It is substantially the same manner as Example 5, the difference is that only:High-temperature ammonolysis process Nano tube array of titanium dioxide, setting
Ammonia concentration is 99.4%, and ammonia flow is 50mL/min, is warming up to 900 DEG C of reaction 1h.
Claims (14)
1. a kind of polypyrrole-titanium dioxide or the coaxial three layers of nanotube array composite material of titanium nitride-polyaniline, its feature exists
In：Titanium dioxide or titanium nitride nano pipe array backbone (1) including pipe wall absolute construction, in titanium dioxide or titanium nitride nano
The polypyrrole nanotube (2) of pipe array backbone (1) outside wall surface aggregation deposition and in titanium dioxide or titanium nitride nano pipe
The polyaniline nanotube (3) of array backbone (1) internal face aggregation deposition；Polypyrrole-the titanium dioxide or titanium nitride-poly-
The coaxial three layers of nanotube array composite material of aniline is that one group of tight ordered arrangement of three layers of nanotube with concentric shafts is formed
Array structure, with concentric shafts three layers of described nanometer outer tube layer are polypyrrole nanotube, and intermediate layer is titanium dioxide or nitrogen
Change titanium nanotube, internal layer is polyaniline nanotube；
The polypyrrole nanotube (2) is using the chemical polymerization nucleation pretreatment under vacuum condition and electrochemistry by polypyrrole
Polyreaction formation of deposits, the polyaniline nanotube (3) is using the chemical polymerization nucleation under hydrothermal condition by polyaniline
Pretreatment and light help electrochemical polymerization reactive deposition to be formed.
2. a kind of polypyrrole-titanium dioxide according to claim 1 or the coaxial three layers of nano-tube array of titanium nitride-polyaniline
Composite, it is characterised in that：The pipe thickness of titanium dioxide or titanium nitride nano pipe is 10-20nm, internal diameter is 80-130nm,
Length is 860-960nm, and distance is 30-68nm between adjacent titanium dioxide or titanium nitride nano pipe；When skeleton is titanium dioxide
During nano-tube array, the pipe thickness of polypyrrole nanotube is 8-15nm, and the pipe thickness of polyaniline nanotube is 8-11nm；When
When skeleton is titanium nitride nano pipe array, the pipe thickness of polypyrrole nanotube is 18-30nm, the thickness of pipe wall of polyaniline nanotube
Spend for 5-15nm.
3. the coaxial three layers of nanometer of a kind of polypyrrole-titanium dioxide or titanium nitride-polyaniline described in any one of claim 1 to 2
The preparation method of pipe array composite material, it is characterised in that：Electrification is helped by chemical polymerization, electrochemical polymerization reaction and light
The substep selectivity synthesis reaction method for learning polyreaction is prepared from, and comprises the following steps：
(1) preparation of Nano tube array of titanium dioxide：Using constant potential anodic oxidation synthetic method, in two electrode chemical reagents
In system, using titanium sheet as anode and as working electrode, using platinized platinum as negative electrode and as auxiliary to electrode, with ammonium fluoride, phosphorus
The mixed aqueous solution of acid, methanol and ethylene glycol reacts 1-3h as reaction electrolyte solution under the conditions of constant voltage 20-30V, makes
Obtain the Nano tube array of titanium dioxide of amorphous state；By the Nano tube array of titanium dioxide of amorphous state in 400-500 DEG C of high temperature
Calcining 1-3h, is obtained the Nano tube array of titanium dioxide of Anatase；
(2) preparation of titanium nitride nano pipe array：Step (1) is obtained the Nano tube array of titanium dioxide of Anatase in pure ammonia
Under the conditions of atmosphere, 900 DEG C of constant temperature nitrogen treatment 1-2h are obtained titanium nitride nano pipe array；
(3) polypyrrole-titanium dioxide of chemical polymerization pretreatment or the polypyrrole-titanium nitride composite material of chemical polymerization pretreatment
Preparation：By Nano tube array of titanium dioxide obtained in step (1) or titanium nitride nano pipe array surface is equal obtained in step (2)
The even carbonic allyl ester solution for smearing pyrroles and ferric chloride, under vacuum condition, 35-45 DEG C of constant temperature processes 6-8min, repeats 3-5
It is secondary, obtain final product the polypyrrole-titanium dioxide of chemical polymerization pretreatment or the polypyrrole-titanium nitride composite wood of chemical polymerization pretreatment
Material；
(4) preparation of polypyrrole-titanium oxide or polypyrrole-titanium nitride composite material：In three-electrode electro Chemical reaction system, with
Polypyrrole-the titanium dioxide of chemical polymerization pretreatment or the polypyrrole-titanium nitride composite material of chemical polymerization pretreatment are work
Electrode, using the Allyl carbonate mixed solution of pyrroles, lithium perchlorate and methanol as reaction electrolyte solution, using step scanning
Voltammetry electrochemical polymerization reaction is obtained polypyrrole-titanium dioxide or polypyrrole-titanium nitride composite material；
(5) polypyrrole-titanium dioxide-polyaniline composite material or the poly- pyrrole of chemical polymerization pretreatment of chemical polymerization pretreatment
Cough up-the preparation of titanium nitride-polyaniline composite material：By polypyrrole-titanium dioxide or polypyrrole-titanium nitride obtained in step (4)
Composite soaks after 5-15min in aniline, the acetonitrile solution of potassium peroxydisulfate, in being inverted in hydrothermal reaction kettle, 55-65 DEG C of perseverance
Warm water heat treatment 1-2h, the polypyrrole-titanium dioxide-polyaniline composite material or chemical polymerization that chemical polymerization pretreatment is obtained is pre-
Polypyrrole-titanium nitride-the polyaniline composite material of process；
(6) preparation of coaxial three layers of nanotube array composite material：In three-electrode electro Chemical reaction system, with step (5) system
Polypyrrole-titanium dioxide-the polyaniline composite material or the polypyrrole-nitrogen of chemical polymerization pretreatment of the chemical polymerization pretreatment for obtaining
Change titanium-polyaniline composite material be working electrode, using aniline, chloro- 2 amino benzoic Acid of 4- and dimethylformamide in water as
Reaction electrolyte solution, under the irradiation of 1000W xenon lamps, helps electrochemical polymerization reaction to be obtained coaxial using ladder water price light
Three layers of nanotube array composite material.
4. a kind of polypyrrole-titanium dioxide according to claim 3 or the coaxial three layers of nano-tube array of titanium nitride-polyaniline
The preparation method of composite, it is characterised in that：In step (1), in reaction electrolyte solution, the molar concentration of ammonium fluoride is
0.15-0.30mol/L, the molar concentration of phosphoric acid are 0.4-0.5mol/L, and the volume fraction of methanol is 5-8%, the body of ethylene glycol
Fraction is 35-45%.
5. a kind of polypyrrole-titanium dioxide according to claim 3 or the coaxial three layers of nano-tube array of titanium nitride-polyaniline
The preparation method of composite, it is characterised in that：In step (1), in reaction electrolyte solution, the molar concentration of ammonium fluoride is
0.2mol/L, the volume fraction that the molar concentration of phosphoric acid is 0.5mol/L, the volume fraction of methanol is 5%, ethylene glycol are 40%.
6. a kind of polypyrrole-titanium dioxide according to claim 3 or the coaxial three layers of nano-tube array of titanium nitride-polyaniline
The preparation method of composite, it is characterised in that：In step (2), pure ammonia atmosphere environment is：Ammonia concentration is 99.0-99.6%,
Ammonia flow is 30-50mL/min；900 DEG C of constant temperature nitrogen treatment programs are：It is warming up to 900 DEG C of constant temperature and processes 1-2h；Intensification journey
Sequence is：It is 5 DEG C/min from room temperature to 300 DEG C, is 2 DEG C/min from 300 to 700 DEG C, is 1 DEG C/min from 700 to 900 DEG C.
7. a kind of polypyrrole-titanium dioxide according to claim 3 or the coaxial three layers of nano-tube array of titanium nitride-polyaniline
The preparation method of composite, it is characterised in that：In step (3), in the carbonic allyl ester solution of pyrroles and ferric chloride, pyrroles
Molar concentration be 0.5-1.5mol/L, the molar concentration of ferric chloride is 0.025-0.030mol/L.
8. a kind of polypyrrole-titanium dioxide according to claim 3 or the coaxial three layers of nano-tube array of titanium nitride-polyaniline
The preparation method of composite, it is characterised in that：In step (3), in the carbonic allyl ester solution of pyrroles and ferric chloride, pyrroles
Molar concentration be 1.0mol/L, the molar concentration of ferric chloride is 0.028mol/L.
9. a kind of polypyrrole-titanium dioxide according to claim 3 or the coaxial three layers of nano-tube array of titanium nitride-polyaniline
The preparation method of composite, it is characterised in that：In step (4), the Allyl carbonate mixing of pyrroles, lithium perchlorate and methanol is molten
In liquid, the molar concentration of pyrroles is 0.15-0.25mol/L, and the molar concentration of lithium perchlorate is 0.05-0.1mol/L, methanol
Volume fraction 3-5%；Ladder water price condition is：Take-off potential is 0.55V, and termination current potential is 1.1V, and current potential increment is
0.001-0.004V/s, the step cycle is 0.1-0.4s, and scanning hop count is 3-6.
10. a kind of polypyrrole-titanium dioxide according to claim 3 or the coaxial three layers of nanotube battle array of titanium nitride-polyaniline
The preparation method of row composite, it is characterised in that：In step (4), the Allyl carbonate mixing of pyrroles, lithium perchlorate and methanol
In solution, the molar concentration of pyrroles is 0.2mol/L, and the molar concentration of lithium perchlorate is 0.075mol/L, the volume fraction of methanol
4%；
A kind of 11. polypyrrole-titanium dioxide according to claim 3 or the coaxial three layers of nanotube battle array of titanium nitride-polyaniline
The preparation method of row composite, it is characterised in that：In step (5), in aniline, the acetonitrile solution of potassium peroxydisulfate, aniline rubs
Your concentration is 0.05-0.15mol/L, the molar concentration of potassium peroxydisulfate is 0.04-0.06mol/L.
A kind of 12. polypyrrole-titanium dioxide according to claim 3 or the coaxial three layers of nanotube battle array of titanium nitride-polyaniline
The preparation method of row composite, it is characterised in that：In step (5), in aniline, the acetonitrile solution of potassium peroxydisulfate, aniline rubs
Your concentration is 0.10mol/L, the molar concentration of potassium peroxydisulfate is 0.05mol/L.
A kind of 13. preparation methoies of coaxial three layers of nanotube array composite material according to claim 3, its feature exists
In：In step (6), in the chloro- 2- amino benzoic Acid of aniline, 4- and dimethylformamide in water, the molar concentration of aniline is
The molar concentration of chloro- 2 amino benzoic Acid of 0.05-0.2mol/L, 4- is 0.3-0.5mol/L, the volume fraction of dimethylformamide
For 5-10%；Ladder water price condition is：Take-off potential is -0.2V, and termination current potential is 1.0V, and current potential increment is 0.001-
0.004V/s, the step cycle is 0.2-0.8s, and scanning hop count is 5-10.
The coaxial three layers of nanometer of a kind of polypyrrole-titanium dioxide or titanium nitride-polyaniline described in 14. any one of claim 1-2
Application in pipe array composite material electrochemical energy storage field.
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| CN105185601B (en) * | 2015-09-28 | 2018-02-23 | 华南理工大学 | A kind of titania nanotube/polyaniline composite electrode and preparation and application |
| CN106449128B (en) * | 2016-09-28 | 2018-05-04 | 东南大学 | Integrated heteropoly acid modification polyaniline/titanium nitride core-shell nano linear array composite material and its preparation method and application |
| CN110491678A (en) * | 2018-05-14 | 2019-11-22 | 深圳市中科摩方科技有限公司 | A kind of material and its preparation method and application of surface electrochemical capacitance modification |
| CN109988303B (en) * | 2019-03-05 | 2021-04-20 | 广西大学 | Nitrogen-doped high-crosslinking hollow nanotube composite material and preparation method thereof |
| CN110504112B (en) * | 2019-08-12 | 2021-06-18 | 三峡大学 | Preparation method of polypyrrole-coated nitrogen-doped titanium dioxide super-microsphere electrode |
| CN111422944A (en) * | 2020-05-19 | 2020-07-17 | 佛山科学技术学院 | Multilayer film material |
| CN114515600B (en) * | 2020-11-18 | 2023-08-11 | 万华化学集团股份有限公司 | Metal hetero element modified titanium nitride-polyaniline catalyst, preparation method and application thereof in synthesizing para-hydroxyanisole |
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